Ethylene copolymer compositions, film and polymerization processes

ABSTRACT

Ethylene copolymers having a relatively high melt flow ratio and a multimodal profile in a temperature rising elution fractionation (TREF) plot are disclosed. The copolymers can be made into film having good dart impact values and good stiffness properties under decreased extruder pressures.

REFERENCE TO RELATED APPLICATION

This application is a Continuation-In-Part of application Ser. No.13/918,506 filed Jun. 14, 2013, entitled “Polyethylene Composition, Filmand Polymerization Process”, which is herein incorporated by referencein its entirety.

FIELD OF THE INVENTION

The preparation of polyethylene copolymers, the films made from them aswell as a polyethylene polymerization process are disclosed herein. Inan embodiment, a phosphinimine type catalyst is employed to makeethylene copolymers having a relatively high melt flow ratio (I₂₁/I₂)and a multimodal TREF profile. The ethylene copolymers have acomposition distribution breadth index CDBI₅₀ of between about 45 wt %and about 75 wt % and can be made into film with good physicalproperties while exhibiting enhanced processability.

BACKGROUND OF THE INVENTION

The search for polyethylene products having an improved balance ofphysical properties and processability has led to the development ofproducts having improved output capacity and ever improving end useproperties such as enhanced film tear or dart impact properties.Particularly useful is the development of polymer architectures forwhich polymer blending strategies can be avoided for enhancement ofpolymer properties, since these strategies increase cost.

U.S. Pat. Appl. No. 2011/0003099 discusses low melt flow ratio (MFR)linear polyethylene and high melt flow ratio (MFR) linear polyethylene,which are distinguished by an I₂₁/I₂ of less than 30 and an I₂₁/I₂ ofgreater than 30 respectively.

Resins having both a narrow molecular weight distribution and a low meltflow ratio are well known and include resins produced with metallocenecatalysts and phosphinimine catalysts. Such resins include for exampleExceed 1018A™ from ExxonMobil and those described in U.S. Pat. No.5,420,220 and Canadian Pat. Appl. No. 2,734,167. These resins can bemade into films having a good balance of physical and opticalproperties, but can be difficult to process in the absence of processingaids, as indicated by, for example, a relatively low output capacity ona blown film line.

Resins having a higher melt flow ratio are more attractive to filmproducers because they are generally easier to process. U.S. Pat. Nos.6,255,426 and 6,476,171 and U.S. Pat. Appl. No. 2011/0003099 eachdescribe the production and use of resins having melt flow ratios whichare in excess of 30 and which have moderately broad molecular weightdistributions. The resins are thought to contain long chain branching.The polymers disclosed in U.S. Pat. Nos. 6,255,426 and 6,476,171 aremade with a bridged bis-indenyl zirconocene catalyst and have acomposition distribution breadth index (CDBI) of greater than 75%. Theresins have been referred to as Enable™ polymers (ExxonMobil) in thepatent literature (see for example, the Example Polymers disclosed inU.S. Pat. Appl. No. 2011/0003099), and although the resins arerelatively easy to process, they also have a good balance of strengthand stiffness properties when blown into film. For example, the filmshad physical properties which were comparable to Exceed 1018A materialsdespite their better shear thinning behavior. The polymers disclosed inU.S. Pat. Appl. No. 2011/0003099, include a new “Enable” grade resinhaving a low melt index (I₂=0.3), a relatively high melt flow ratio(I₂₁/I₂ is from 46-58) and a moderately broad molecular weightdistribution (e.g. M_(w)/M_(n) is 3.4). The polymers also have a singlepeak in a TREF profile, with a T(75)−T(25) of less than 4° C.

Manipulation of the comonomer distribution profile has also providednovel ethylene copolymer architectures in an effort to improve thebalance between physical properties and polymer processability.

It is generally the case that metallocene catalysts and other so called“single site catalysts” typically incorporate comonomer more evenly thantraditional Ziegler-Natta catalysts when used for catalytic ethylenecopolymerization with alpha olefins. This fact is often demonstrated bymeasuring the composition distribution breadth index (CDBI) forcorresponding ethylene copolymers. The definition of compositiondistribution breadth index (CDBI₅₀) can be found in PCT publication WO93/03093 and in U.S. Pat. No. 5,206,075. The CDBI₅₀ is convenientlydetermined using techniques which isolate polymer fractions based ontheir solubility (and hence their comonomer content). For example,temperature rising elution fractionation (TREF) as described by Wild etal. J. Poly. Sci., Poly. Phys. Ed. Vol. 20, p441, 1982 can be employed.From the weight fraction versus composition distribution curve, theCDBI₅₀ is determined by establishing the weight percentage of acopolymer sample that has a comonomer content within 50% of the mediancomonomer content on each side of the median. Generally, Ziegler-Nattacatalysts produce ethylene copolymers with a CDBI₅₀ lower than that of asingle site catalyst at a similar density consistent with aheterogeneously branched copolymer. Typically, a plurality of prominentpeaks is observed for such polymers in a TREF (temperature raisingelution fractionation) analysis. Such peaks are consistent with thepresence of heterogeneously branched material which generally includes ahighly branched fraction, a medium branched fraction and a higherdensity fraction having little or no short chain branching. In contrast,metallocenes and other single site catalysts, will most often produceethylene copolymers having a CDBI₅₀ higher than that of a Ziegler-Nattacatalyst at similar density and which often contain a single prominentpeak in a TREF analysis, consistent with a homogeneously branchedcopolymer.

Despite the forgoing, methods have been developed to access polyethylenecopolymer compositions having a broadened comonomer distribution (i.e.more Ziegler-Natta like) while otherwise maintaining productcharacteristics typical of metallocene and single site catalyst resin,such as high dart impact strength for blown film. Such resins can bemade, for example, by using a mixture of metallocene catalysts in asingle reactor, using a plurality of polymerization reactors underdifferent polymerization conditions, or by blending metallocene producedethylene copolymers.

U.S. Pat. Nos. 5,382,630, 5,382,631 and WO 93/03093 describepolyethylene copolymer blend compositions having broad or narrowmolecular weight distributions, and broad or narrow comonomerdistributions. For example a blend may have a narrow molecular weightdistribution, while simultaneously having a bimodal compositiondistribution. Alternatively a blend may have a broad molecular weightdistribution while simultaneously having a unimodal compositiondistribution. The blends are made by melt blending two polyethyleneresins with similar or different molecular weights and similar ordifferent comonomer contents, where each resin is formed using ametallocene catalyst in a gas phase reactor.

U.S. Pat. No. 7,018,710 discloses blends comprising a high molecularweight component having a high comonomer content and a low molecularweight component having a low comonomer content. The ethylene copolymerblend, which arises from the use of a metallocene catalyst in a cascadedual reactor process where each reactor is operated under differentconditions (e.g. a cascade slurry phase-gas phase reactor), shows twodistinct maxima in a TREF fractogram. The polymers were applied as asealing layer in a heat sealable film.

A mixed catalyst system containing a “poor comonomer incorporator” and a“good comonomer incorporator” is disclosed in U.S. Pat. Nos. 6,828,394and 7,141,632. The poor comonomer incorporating catalyst may be ametallocene having at least one fused ring cyclopentadienyl ligand, suchas an indenyl ligand, with appropriate substitution (e.g. alkylsubstitution at the 1-position). The good comonomer incorporatingcatalyst was selected from an array of well-known metallocenes and whichwas generally less sterically encumbered toward the front end of themolecule than the poor comonomer incorporator. These mixed catalystsystems produced polyethylene copolymers having a bimodal TREFdistribution in which two elution peaks are well separated from oneanother, consistent with the presence of higher and lower densitycomponents. The mixed catalysts also produced ethylene copolymer havinga broadened molecular weight distribution relative to ethylene copolymermade with either one of the single metallocene component catalysts.

A mixed catalyst system comprising three distinct metallocene catalystsis disclosed in U.S. Pat. No. 6,384,158. Ethylene copolymers havingbroadened molecular weight distributions were obtained when using thesecatalyst systems to polymerize ethylene with an alpha olefin such as1-hexene.

U.S. Pat Appl. No. 2011/0212315 describes a linear ethylene copolymerhaving a bimodal or multimodal comonomer distribution profile asmeasured using DSC, TREF or CRYSTAF techniques. The copolymers maintaina high dart impact resistance when blown into film and are relativelyeasy to process as indicated by a reduced shear thinning index, relativeto ethylene copolymers having a unimodal comonomer distribution profile.The exemplified ethylene copolymer compositions, which have a melt flowratio of less than 30, are made in a single gas phase reactor byemploying a mixed catalyst system comprising a metallocene catalyst anda late transition metal catalyst.

U.S. Pat. No. 7,534,847 demonstrates that use of a chromium basedtransition metal catalyst gives an ethylene copolymer having a bimodalcomonomer distribution (as indicated by CRYSTAF) with a CDBI of lessthan 50 wt % (see Table 1 of U.S. Pat. No. 7,534,847). The patentteaches that the copolymers may have a molecular weight distribution offrom 1 to 8, significant amounts of vinyl group unsaturation, long chainbranching and specific amounts of methyl groups as measured by CRYSTAFfractionation.

U.S. Pat. No. 6,932,592 describes very low density (i.e. <0.916 g/cc)ethylene copolymers produced with a bulky non-bridged bis-Cp metallocenecatalyst. A preferred metallocene isbis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride. Theexamples show that in the gas phase, supported versions of this catalystproduce copolymer from ethylene and 1-hexene which has a CDBI of between60 and 70% and a bimodal comonomer distribution as measured bytemperature raising elution fractionation (TREF).

U.S. Pat. No. 6,420,507 describes a low density ethylene copolymerhaving a narrow molecular weight distribution (i.e. 1.5 to 3.0) and abimodal TREF profile. The polymerization is carried out in the gas phaseusing a so called “constrained geometry” catalyst having an indenylligand.

U.S. Pat. Nos. 6,248,845, 6,528,597, 7,381,783 and U.S. Pat. Appl. No.2008/0108768 disclose that a bulky ligand metallocene based on hafniumand a small amount of zirconium can be used to provide anethylene/1-hexene copolymer which has a bimodal TREF profile. It istaught that the hafnium chloride precursor compounds used to synthesizethe bulky metallocene catalysts are either contaminated with smallamount of zirconium chloride or that zirconium chloride may bedeliberately added. The amounts of zirconium chloride present range from0.1 mol % to 5 mol %. Hence, the final hafnocene catalysts contain smallamounts (i.e. 0.1 to 5 mol %) of their zirconocene analogues. Sincezirconium based catalysts can have superior activity relative to theirhafnium analogs it is possible that the products made have a significantcontribution from the zirconocene species. If this is the case, then itis perhaps not surprising that a bimodal TREF profile results. Thepatent provides data for cast and blown film applications which showsthat compared to Exceed type resins, the polymers are more easilyextruded, with lower motor load, higher throughput and reduced headpressure. The resins give cast film with high tear values and blown filmwith high dart impact values.

U.S. Pat. Nos. 6,956,088, 6,936,675, 7,179,876 and 7,172,816 disclosethat use of a “substantially single” bulky ligand hafnium catalystprovides an ethylene copolymer composition having a CDBI of below 55%,especially below 45% as determined by CRYSTAF. Recall, that hafnocenecatalysts derived from hafnium chloride are expected to have zirconocenecontaminants present in low amounts. U.S. Pat. Nos. 6,936,675 and7,179,876 further teach that the CDBI could be changed under differenttemperature conditions when using hafnocene catalysts. Polymerization atlower temperatures gave ethylene copolymer having a broader compositiondistribution breadth index (CDBI) relative to polymers obtained athigher temperatures. For example, use of the catalystsbis(n-propylcyclopentadienyl)hafnium dichloride orbis(n-propylcyclopentadienyl)hafnium difluoride in a gas phase reactorfor the copolymerization of ethylene and 1-hexene at ≦80° C., gavecopolymers having a CDBI of between 20 and 35%, compared to CDBI valuesof between 40 and 50% for copolymers obtained at 85° C. The polymersdisclosed can, under certain draw down ratios, provide films having amachine direction tear value of greater than 500 g/mil, a dart impactresistance of greater than 500 g/mil, as well as good stiffness. Thepolymers also have good processability.

U.S. Pat. No. 5,281,679 describes bis-cyclopentadienyl metallocenecatalysts which have secondary or tertiary carbon substituents on acylcopentadienyl ring. The catalysts provide polyethylene materials withbroadened molecular weight during gas phase polymerization.

Cyclic bridged bulky ligand metallocene catalysts are described in U.S.Pat. Nos. 6,339,134 and 6,388,115 which give easier processing ethylenepolymers.

A hafnocene catalyst is used in U.S. Pat. No. 7,875,690 to give anethylene copolymer in a gas phase fluidized bed reactor. The copolymerhas a so called “broad orthogonal composition distribution” whichimparts improved physical properties and low extractables. A broadorthogonal composition distribution is one in which the comonomer isincorporated predominantly in the high molecular weight chains. Thecopolymers had a density of at least 0.927 g/cc. Polyethylene copolymershaving a similarly broad orthogonal composition distribution but a lowerdensity are disclosed in U.S. Pat. No. 8,084,560 and U.S. Pat. Appl. No.2011/0040041A1. Again a hafnocene catalyst is employed in a gas phasereactor to give the ethylene copolymer.

U.S. Pat. No. 5,525,689 also discloses the use of a hafnium basedmetallocene catalyst for use in olefin polymerization. The polymers hada ratio of I₁₀/I₂ of from 8 to 50, a density of from 0.85 to 0.92 g/cc,a Mw/Mn of up to 4.0, and were made in the gas phase.

U.S. Pat. No. 8,114,946 discloses ethylene copolymers which have amolecular weight distribution (M_(w)/M_(n)) ranging from 3.36 to 4.29, areversed comonomer incorporation and contain low levels of long chainbranching. The melt flow ratios of the disclosed polymers are generallybelow about 30. A bridged cyclopentadienyl/fluorenyl metallocenecatalyst having an unsaturated pendant group is used to make theethylene copolymers. The patent application does not mention films orfilm properties.

U.S. Pat. No. 6,469,103 discusses ethylene copolymer compositionscomprising a first and a second ethylene copolymer component. Theindividual components are defined using ATREF-DV analytical methodswhich show a bimodal or multimodal structure with respect to comonomerplacement. The compositions have an I₁₀/I₂ value of greater 6.6 and arelatively narrow molecular weight distribution (i.e. M_(W)/M_(n) isless than or equal to 3.3) consistent with the presence of long chainbranching. The polymers are made using a dual solution reactor systemwith mixed catalysts.

A process for making ethylene polymer compositions involving the use ofat least two polymerization reactors is described in U.S. Pat. No.6,319,989. The ethylene copolymers have a molecular weight distributionof greater than 4.0 and show two peaks when subjected to acrystallization analysis fractionation (CRYSTAF).

U.S. Pat. No. 6,462,161 describes the use of either a constrainedgeometry type catalyst or a bridged bis-Cp metallocene catalyst toproduce, in a single reactor, a polyolefin composition having long chainbranching and a molecular weight maximum occurring in the part of thecomposition having the highest comonomer content (i.e. a reversedcomonomer distribution). The compositions made with a constrainedgeometry catalyst have multimodal TREF profiles, and relatively narrowmolecular weight distributions (e.g. the exemplified resins have aM_(w)/M_(n) of from 2.19 to 3.4, see Table 1 in the examples section ofU.S. Pat. No. 6,462,161). The compositions made with a bridged bis-Cpmetallocene catalyst have complex TREF profiles and somewhat broadermolecular weight distribution (e.g. the exemplified reins have aM_(w)/M_(n) of 3.43 or 6.0, see Table 1 in the Examples section of U.S.Pat. No. 6,462,161).

Ethylene copolymers are taught in U.S. Pat. No. 7,968,659 which have amelt index of from 1.0 to 2.5, a M_(w)/M_(n) of from 3.5 to 4.5, a meltelastic modulus G′ (G″=500 Pa) of from 40 to 150 Pa and an activationenergy of flow (Ea) in the range of 28 to 45 kJ/mol. Constrainedgeometry catalysts are used to make the polymer compositions in the gasphase.

U.S. Pat. No. 7,521,518 describes the use of a constrained geometrycatalyst to give an ethylene copolymer composition having a reversedcomonomer distribution as determined by various cross fractionationchromatography (CFC) parameters and a molecular weight distribution offrom 2 to 10.

U.S. Pat. No. 5,874,513 describes that the use of a mixture ofcomponents which give rise to a supported metallocene catalyst can, in agas phase reactor, give an ethylene copolymer with reduced comonomerdistribution homogeneity. The patent defines a composition distributionparameter Cb which is representative of the distribution of comonomerswithin the polymer composition. The TREF analysis of the copolymercomposition showed a bimodal distribution.

U.S. Pat. No. 6,441,116 discloses a film comprising an ethylenecopolymer with a composition distribution curve obtained by TREF havingfour distinct areas including one peak defining area which is attributedto a highly branched component.

An ethylene/alpha olefin copolymer produced with a Ziegler-Nattacatalyst and having greater than about 17 weight percent of a highdensity fraction, as determined by analytical TREF methods, and amolecular weight distribution (M_(w)/M_(n)) of less than about 3.6 isdisclosed in U.S. Pat. No. 5,487,938. The high density fraction haslittle short chain branching, while the balance of the copolymercomposition is referred to as the fraction containing short chainbranching. Hence, the data is consistent with a bimodal distribution ofcomonomer incorporation into the ethylene copolymer.

U.S. Pat. No. 6,642,340 describes an ethylene copolymer having aspecific relationship between a melt flow rate and melt tension. Thepolymers further comprise between 0.5 and 8 wt % of a component elutingat not lower than 100° C. in a TREF analysis.

Use of phosphinimine catalysts for gas phase olefin polymerization isthe subject matter of U.S. Pat. No. 5,965,677. The phosphiniminecatalyst is an organometallic compound having a phosphinimine ligand, acyclopentadienyl type ligand and two activatable ligands, and which issupported on a suitable particulate support such as silica. Theexemplified catalysts had the formula CpTi(N═P(tBu)₃)X₂ where X was Cl,Me or Cl and —O-(2,6-iPr-C₆H₃).

In co-pending CA Pat. Appl. No. 2,734,167 we showed that suitablysubstituted phosphinimine catalysts gave narrow molecular weightdistribution copolymers which when made into film showed a good balanceof optical and physical properties.

Polymers and films made in the gas phase using various single sitecatalysts, including so called “phosphinimine” catalysts, were disclosedat Advances in Polyolefins II, Napa, Calif.—October 24-27, 1999(“Development of NOVA's Single Site Catalyst Technology for use in theGas Phase Process”—I. Coulter; D. Jeremic; A. Kazakov; I. McKay).

In a disclosure made at the 2002 Canadian Society for ChemistryConference (“Cyclopentadienyl Phosphinimine TitaniumCatalysts—Structure, Activity and Product Relationships in HeterogeneousOlefin Polymerization.” R. P. Spence; I. McKay; C. Carter; L. Koch; D.Jeremic; J. Muir; A. Kazakov. NOVA Research and Technology Center, CIC,2002), it was shown that phosphinimine catalysts bearing variouslysubstituted cyclopentadienyl and indenyl ligands were active toward thegas phase polymerization of ethylene when in supported form.

U.S. Pat. Appl. No. 2008/0045406, discloses a supported phosphiniminecatalyst comprising a C₆F₅ substituted indenyl ligand. The catalyst wasactivated with an ionic activator having an active proton for use in thepolymerization of ethylene with 1-hexene.

U.S. Pat. Appl. No. 2006/0122054 discloses the use of a dual catalystformulation one component of which is a phosphinimine catalyst having ann-butyl substituted indenyl ligand. The patent is directed to theformation of bimodal resins suitable for application in pipe.

SUMMARY OF THE INVENTION

We now report that a polymerization catalyst system comprising a singlephosphinimine catalyst can provide an ethylene copolymer having amultimodal comonomer distribution profile and medium molecular weightdistribution when used in a single reactor. Embodiments of the inventionmitigate the need for polymer blends, mixed catalysts, or mixed reactortechnologies in the formation of polyethylene resin which is easy toprocess and has a good balance of physical properties.

Provided in one embodiment is an ethylene copolymer comprising ethyleneand an alpha olefin having 3-8 carbon atoms, the copolymer having adensity of from about 0.916 g/cc to about 0.936 g/cc, a melt index (I₂)of from about 0.1 g/10 min to about 2.0 g/10 min, a melt flow ratio(I₂₁/I₂) of from about 32 to about 50, a molecular weight distribution(M_(w)/M_(n)) of from about 3.6 to about 6.5, a reverse comonomerdistribution profile as determined by GPC-FTIR, a multimodal TREFprofile, a composition distribution breadth index CDBI₅₀ of from about45 wt % to about 75 wt % as determined by TREF, and which satisfies thefollowing relationship: (M_(w)/M_(n))≧72 [(I₂₁/I₂)⁻¹+10⁻⁶ (M_(n))].

Provided in one embodiment is an ethylene copolymer comprising ethyleneand an alpha olefin having 3-8 carbon atoms, the copolymer having adensity of from about 0.916 g/cc to about 0.936 g/cc, a melt index (I₂)of from about 0.1 g/10 min to about 2.0 g/10 min, a melt flow ratio(I₂₁/I₂) of from about 32 to about 50, a molecular weight distribution(M_(w)/M_(n)) of from about 3.6 to about 6.5, a reverse comonomerdistribution profile as determined by GPC-FTIR, a multimodal TREFprofile, a composition distribution breadth index CDBI₅₀ of from about45 wt % to about 75 wt % as determined by TREF, and which satisfies thefollowing relationships: (M_(w)/M_(n))≧about 72 [(I₂₁/I₂)⁻¹+10⁻⁶(M_(n))] and δ^(XO) is from about 55° to about 70°. Provided in oneembodiment is an ethylene copolymer comprising ethylene and an alphaolefin having 3-8 carbon atoms, the copolymer having a density of fromabout 0.916 g/cc to about 0.936 g/cc, a melt index (I₂) of from about0.1 g/10 min to about 2.0 g/10 min, a melt flow ratio (I₂₁/I₂) of fromabout 32 to about 50, a molecular weight distribution (M_(w)/M_(n)) offrom about 3.6 to about 6.5, a reverse comonomer distribution profile asdetermined by GPC-FTIR, a multimodal TREF profile, a compositiondistribution breadth index CDBI₅₀ of from about 45 wt % to about 75 wt %as determined by TREF, and which satisfies the following relationships:(M_(w)/M_(n))≧72 [(I₂₁/I₂)⁻¹+10⁻⁶ (M_(n))]; and δ^(XO)≦83.0−1.25(CDBI₅₀)/(M_(w)/M_(n)).

Provided in one embodiment is an ethylene copolymer comprising ethyleneand an alpha olefin having 3-8 carbon atoms, the copolymer having adensity of from about 0.916 g/cc to about 0.936 g/cc, a melt index (I₂)of from about 0.1 g/10 min to about 2.0 g/10 min, a melt flow ratio(I₂₁/I₂) of from about 32 to about 50, a molecular weight distribution(M_(w)/M_(n)) of from about 3.6 to about 6.5, a reverse comonomerdistribution profile as determined by GPC-FTIR, a multimodal TREFprofile, a composition distribution breadth index CDBI₅₀ of from about45 wt % to about 75 wt % as determined by TREF, and which satisfies thefollowing relationships: (M_(w)/M_(n))≧72 [(I₂₁/I₂)⁻¹+10⁻⁶ (M_(n))]; andδ^(XO)≦80.7−(CDBI₅₀)/(M_(w)/M_(n)) at a δ^(XO) of from about 55° toabout 70°.

Provided in one embodiment is an ethylene copolymer comprising ethyleneand an alpha olefin having 3-8 carbon atoms, the copolymer having adensity of from about 0.916 g/cc to about 0.936 g/cc, a melt index (I₂)of from about 0.1 g/10 min to about 2.0 g/10 min, a melt flow ratio(I₂₁/I₂) of from about 32 to about 50, a molecular weight distribution(M_(w)/M_(n)) of from about 3.6 to about 6.5, a reverse comonomerdistribution profile as determined by GPC-FTIR, a multimodal TREFprofile, a composition distribution breadth index CDBI₅₀ of from about45 wt % to about 75 wt % as determined by TREF, and which satisfies thefollowing relationships: (M_(w)/M_(n))≧72 [(I₂₁/I₂)⁻¹+10⁻⁶ (M_(n))];δ^(XO)≦80.7−(CDBI₅₀)/(M_(w)/M_(n)) at a δ^(XO) of from about 50° toabout 70°; and δ^(XO)≦83.0−1.25 (CDBI₅₀)/(M_(w)/M_(n)).

Provided in another embodiment is an olefin polymerization process toproduce an ethylene copolymer, the process comprising contactingethylene and at least one alpha olefin having from 3-8 carbon atoms witha polymerization catalyst system in a single gas phase reactor; theethylene copolymer having a density of from about 0.916 g/cc to about0.936 g/cc, a melt index (I₂) of from about 0.1 g/10 min to about 2.0g/10 min, a melt flow ratio (I₂₁/I₂) of from about 32 to about 50, amolecular weight distribution (M_(w)/M_(n)) of from about 3.6 to about6.5, a reverse comonomer distribution profile as determined by GPC-FTIR,a multimodal TREF profile, a composition distribution breadth indexCDBI₅₀ of from about 45 wt % to about 75 wt % as determined by TREF, andwhich satisfies the following relationship: (M_(w)/M_(n))≧about 72[(I₂₁/I₂)⁻¹+10⁻⁶ (M_(n))]; wherein the polymerization catalyst systemcomprises a single transition metal catalyst, a support, a catalystactivator, and a catalyst modifier; and wherein the single transitionmetal catalyst is a group 4 organotransition metal catalyst.

Provided in another embodiment is an olefin polymerization process toproduce an ethylene copolymer, the process comprising contactingethylene and at least one alpha olefin having from 3-8 carbon atoms witha polymerization catalyst system in a single gas phase reactor; theethylene copolymer having a density of from about 0.916 g/cc to about0.936 g/cc, a melt index (I₂) of from about 0.1 g/10 min to about 2.0g/10 min, a melt flow ratio (I₂₁/I₂) of from about 32 to about 50, amolecular weight distribution (M_(w)/M_(n)) of from about 3.6 to about6.5, a reverse comonomer distribution profile as determined by GPC-FTIR,a multimodal TREF profile, a composition distribution breadth indexCDBI₅₀ of from about 45 wt % to about 75 wt % as determined by TREF, andwhich satisfies the following relationships: (M_(w)/M_(n))≧72[(I₂₁/I₂)⁻¹+10⁻⁶ (M_(n))]; and δ^(XO)≦83.0−1.25 (CDBI₅₀)/(M_(w)/M_(n));wherein the polymerization catalyst system comprises a single transitionmetal catalyst, a support, a catalyst activator, and a catalystmodifier; and wherein the single transition metal catalyst is a group 4organotransition metal catalyst.

Provided in another embodiment is an olefin polymerization process toproduce an ethylene copolymer, the process comprising contactingethylene and at least one alpha olefin having from 3-8 carbon atoms witha polymerization catalyst system in a single gas phase reactor; theethylene copolymer having a density of from about 0.916 g/cc to about0.936 g/cc, a melt index (I₂) of from about 0.1 g/10 min to about 2.0g/10 min, a melt flow ratio (I₂₁/I₂) of from about 32 to about 50, amolecular weight distribution (M_(w)/M_(n)) of from about 3.6 to about6.5, a reverse comonomer distribution profile as determined by GPC-FTIR,a multimodal TREF profile, a composition distribution breadth indexCDBI₅₀ of from about 45 wt % to about 75 wt % as determined by TREF, andwhich satisfies the following relationships: (M_(w)/M_(n))≧about 72[(I₂₁/I₂)⁻¹+10⁻⁶ (M_(n))]; and δ^(XO)≦about 80.7−(CDBI₅₀)/(M_(w)/M_(n))at a δ^(XO) of from about 55° to about 70°; wherein the polymerizationcatalyst system comprises a single transition metal catalyst, a support,a catalyst activator, and a catalyst modifier; and wherein the singletransition metal catalyst is a group 4 organotransition metal catalyst.

Provided in another embodiment is an olefin polymerization process toproduce an ethylene copolymer, the process comprising contactingethylene and at least one alpha olefin having from 3-8 carbon atoms witha polymerization catalyst system in a single gas phase reactor; theethylene copolymer having a density of from about 0.916 g/cc to about0.936 g/cc, a melt index (I₂) of from about 0.1 g/10 min to about 2.0g/10 min, a melt flow ratio (I₂₁/I₂) of from about 32 to about 50, amolecular weight distribution (M_(w)/M_(n)) of from about 3.6 to about6.5, a reverse comonomer distribution profile as determined by GPC-FTIR,a multimodal TREF profile, a composition distribution breadth indexCDBI₅₀ of from about 45 wt % to about 75 wt % as determined by TREF, andwhich satisfies the following relationships: (M_(w)/M_(n))≧72[(I₂₁/I₂)⁻¹+10⁻⁶ (M_(n))]; δ^(XO)≦80.7−(CDBI₅₀)/(M_(w)/M_(n)) at aδ^(XO) of from about 55° to about 70°; and δ^(XO)≦83.0−1.25(CDBI₅₀)/(M_(w)/M_(n)); wherein the polymerization catalyst systemcomprises a single transition metal catalyst, a support, a catalystactivator, and a catalyst modifier; and wherein the single transitionmetal catalyst is a group 4 organotransition metal catalyst.

Provided in another embodiment is a film layer having a dart impact ofgreater than about 200 g/mil, a 1% MD secant modulus of greater than 140MPa, a 1% TD secant modulus of greater than 175 MPa and a ratio of MDtear to TD tear of about 0.75 or less, wherein the film layer comprisesan ethylene copolymer having a density of from about 0.916 g/cc to about0.930 g/cc, a melt index (I₂) of from about 0.1 g/10 min to about 2.0g/10 min, a melt flow ratio (I₂₁/I₂) of from about 32 to about 50, amolecular weight distribution (M_(w)/M_(n)) of from about 3.6 to about6.5, a reverse comonomer distribution profile as determined by GPC-FTIR,a multimodal TREF profile, a composition distribution breadth indexCDBI₅₀ of from about 50 wt % to about 75 wt % as determined by TREF, andwhich satisfies the following relationship: (M_(w)/M_(n))≧72[(I₂₁/I₂)⁻¹+10⁻⁶ (M_(n))].

Provided in another embodiment is a film layer having a dart impact ofgreater than about 200 g/mil, a 1% MD secant modulus of greater than 140MPa, a 1% TD secant modulus of greater than 175 MPa and a ratio of MDtear to TD tear of about 0.75 or less, wherein the film layer comprisesan ethylene copolymer having a density of from about 0.916 g/cc to about0.930 g/cc, a melt index (I₂) of from about 0.1 g/10 min to about 2.0g/10 min, a melt flow ratio (I₂₁/I₂) of from about 32 to about 50, amolecular weight distribution (M_(w)/M_(n)) of from about 3.6 to about6.5, a reverse comonomer distribution profile as determined by GPC-FTIR,a multimodal TREF profile, a composition distribution breadth indexCDBI₅₀ of from about 50 wt % to about 75 wt % as determined by TREF, andwhich satisfies the following relationships: (M_(w)/M_(n))≧72[(I₂₁/I₂)⁻¹+10⁻⁶ (M_(n))]; and δ^(XO)≦83.0−1.25 (CDBI₅₀)/(M_(w)/M_(n)).

Provided in another embodiment is a film layer having a dart impact ofgreater than about 200 g/mil, a 1% MD secant modulus of greater than 140MPa, a 1% TD secant modulus of greater than 175 MPa and a ratio of MDtear to TD tear of about 0.75 or less, wherein the film layer comprisesan ethylene copolymer having a density of from about 0.916 g/cc to about0.930 g/cc, a melt index (I₂) of from about 0.1 g/10 min to about 2.0g/10 min, a melt flow ratio (I₂₁/I₂) of from about 32 to about 50, amolecular weight distribution (M_(w)/M_(n)) of from about 3.6 to about6.5, a reverse comonomer distribution profile as determined by GPC-FTIR,a multimodal TREF profile, a composition distribution breadth indexCDBI₅₀ of from about 50 wt % to about 75 wt % as determined by TREF, andwhich satisfies the following relationships: (M_(w)/M_(n))≧72[(I₂₁/I₂)⁻¹+10⁻⁶ (M_(n))]; and δ^(XO)≦80.7−(CDBI₅₀)/(M_(w)/M_(n)) at aδ^(XO) of from about 55° to about 70°.

Provided in another embodiment is a film layer having a dart impact ofgreater than about 200 g/mil, a 1% MD secant modulus of greater than 140MPa, a 1% TD secant modulus of greater than 175 MPa and a ratio of MDtear to TD tear of about 0.75 or less, wherein the film layer comprisesan ethylene copolymer having a density of from about 0.916 g/cc to about0.930 g/cc, a melt index (I₂) of from about 0.1 g/10 min to about 2.0g/10 min, a melt flow ratio (I₂₁/I₂) of from about 32 to about 50, amolecular weight distribution (M_(w)/M_(n)) of from about 3.6 to about6.5, a reverse comonomer distribution profile as determined by GPC-FTIR,a multimodal TREF profile, a composition distribution breadth indexCDBI₅₀ of from about 50 wt % to about 75 wt % as determined by TREF, andwhich satisfies the following relationships: (M_(w)/M_(n))≧72[(I₂₁/I₂)⁻¹+10⁻⁶ (M_(n))]; δ^(XO)≦80.7−(CDBI₅₀)/(M_(w)/M_(n)) at aδ^(XO) of from about 55° to about 70°; and δ^(XO)≦83.0−1.25(CDBI₅₀)/(M_(w)/M_(n)).

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1A shows a temperature rising elution fractionation (TREF) analysisand profile of an ethylene copolymer made according to one embodiment ofthe present invention.

FIG. 1B shows a temperature rising elution fractionation (TREF) analysisand profile of an ethylene copolymer made according to one embodiment ofthe present invention.

FIG. 2 shows a gel permeation chromatograph (GPC) with refractive indexdetection, of an ethylene copolymer made according to one embodiment ofthe present invention.

FIG. 3 shows a gel permeation chromatograph with Fourier transforminfra-red (GPC-FTIR) detection obtained for an ethylene copolymer madeaccording to one embodiment of the present invention. The comonomercontent, shown as the number of short chain branches per 1000 carbons(y-axis), is given relative to the copolymer molecular weight (x-axis).The upwardly sloping line (from left to right) is the short chainbranching (in short chain branches per 1000 carbons atoms) determined byFTIR. As can be seen in the Figure, the number of short chain branchesincreases at higher molecular weights, and hence the comonomerincorporation is said to be “reversed”.

FIG. 4A show plots of the phase angle vs the complex modulus and thephase angle vs complex viscosity for comparative ethylene copolymerresins no. 1 and 2 as determined by dynamic mechanical analysis (DMA).

FIG. 4B show plots of the phase angle vs the complex modulus and thephase angle vs complex viscosity for inventive ethylene copolymer no. 1and for comparative ethylene copolymers no. 3 and 7, as determined byDMA.

FIG. 5 shows a plot of the equation: Mw/Mn=72 [(I₂₁/I₂)⁻¹+10⁻⁶ (M_(n))].The values from the equation 72 [(I₂₁/I₂)⁻¹+10⁻⁶ (M_(n))] (the y-axis)are plotted against the corresponding Mw/Mn values (the x-axis) forinventive resins 1-6 as well as for several commercially availableresins which have a melt index I₂ of 1.5 g/10 min or less and a densityof between about 0.916 and about 0.930 g/cm³.

FIG. 6 shows a plot of the equation: δ^(XO)=83−1.25(CDBI₅₀/(M_(w)/M_(n)). The values of the equation 80−1.25(CDBI₅₀/(M_(w)/M_(n)) (the x-axis) are plotted against the correspondingcrossover phase angle (δ^(XO)) values (the y-axis) for inventive resins1-6 as well as for several commercially available resins which have amelt index I₂ of 1.5 g/10 min or less and a density of between about0.916 and about 0.930 g/cm³.

FIG. 7 shows a plot of the equation: δ^(XO)=80.7−(CDBI₅₀/(M_(w)/M_(n)).The values of the equation 80.7−(CDBI₅₀/(M_(w)/M_(n)) (the x-axis) areplotted against the corresponding crossover phase angle (δ^(XO)) values(the y-axis) for inventive resins 1-6 as well as for severalcommercially available resins which have a melt index I₂ of 1.5 g/10 minor less and a density of between about 0.916 and about 0.930 g/cm³. Thebroken lines show which resins have a δ^(XO) value of between about 55°and about 70°.

DETAILED DESCRIPTION

Other than in the operating examples or where otherwise indicated, allnumbers or expressions referring to quantities of ingredients, reactionconditions, etc. used in the specification and claims are to beunderstood as modified in all instances by the term “about.”Accordingly, unless indicated to the contrary, the numerical parametersset forth in the following specification and attached claims areapproximations that can vary depending upon the desired properties,which the present invention desires to obtain. At the very least, andnot as an attempt to limit the application of the doctrine ofequivalents to the scope of the claims, each numerical parameter shouldat least be construed in light of the number of reported significantdigits and by applying ordinary rounding techniques.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the invention are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical values, however, inherently contain certainerrors necessarily resulting from the standard deviation found in theirrespective testing measurements.

Also, it should be understood that any numerical range recited herein isintended to include all sub-ranges subsumed therein. For example, arange of “1 to 10” is intended to include all sub-ranges between andincluding the recited minimum value of 1 and the recited maximum valueof 10; that is, having a minimum value equal to or greater than 1 and amaximum value of equal to or less than 10. Because the disclosednumerical ranges are continuous, they include every value between theminimum and maximum values. Unless expressly indicated otherwise, thevarious numerical ranges specified in this application areapproximations.

All compositional ranges expressed herein are limited in total to and donot exceed 100 percent (volume percent or weight percent) in practice.Where multiple components can be present in a composition, the sum ofthe maximum amounts of each component can exceed 100 percent, with theunderstanding that, and as those skilled in the art readily understand,that the amounts of the components actually used will conform to themaximum of 100 percent.

Provided herein are ethylene copolymers having a relatively high meltflow ratio and a multimodal profile in a temperature rising elutionfractionation (TREF) plot. The copolymers can be made into film havinghigh dart impact values and good stiffness properties under decreasedextruder pressures and at good output rates.

Polymerization Catalyst System

The polymerization catalyst system used in embodiments of the presentinvention will comprise a single transition metal catalyst, but maycomprise further components such as but not limited to a support(s),catalyst activator(s), and catalyst modifier(s). The term “singletransition metal catalyst” and similar terms means that duringpreparation of the polymerization catalyst system, only one type ofactive transition metal catalyst is included, and excludespolymerization catalyst systems which comprise two or more differentactive transition metal catalysts such as mixed catalysts and dualcatalysts.

In some embodiments, the transition metal catalyst is an organometalliccatalyst based on a group 4 transition metal. By organometallic catalystit is meant that the catalyst will have at least one ligand within thetransition metal coordination sphere which is bonded to the metal via atleast one carbon-metal bond. Such catalysts may collectively be called“organotransition metal catalysts” or “group 4 organotransition metalcatalysts” when based on a group 4 metal.

In some embodiments, the organotransition metal catalyst is a singlesite catalyst based on a group 4 metal (where the number refers tocolumns in the Periodic Table of the Elements using IUPAC nomenclature).This includes titanium, hafnium and zirconium. The organotransitionmetal catalysts can be group 4 metal complexes in their highestoxidation state.

An example organotransition metal catalyst that is useful in anembodiment of the present invention is a group 4 organotransition metalcatalyst further comprising a phosphinimine ligand. Any organometalliccatalyst/compound/complex having a phosphinimine ligand and which can beused to make the copolymer compositions further defined and describedbelow (in the section titled “The Ethylene Copolymer Composition”) arecontemplated for use. In one embodiment, organotransition metalcatalysts having at least one phosphinimine ligand and which are activein the polymerization of olefins to polymers are termed “phosphiniminecatalysts.”

Transition metal catalysts are usually activated by one or morecocatalytic or catalyst activator species in order to provide polymer.Hence, transition metal polymerization catalysts are sometimes called“pre-catalysts”.

In an embodiment of the invention, the phosphinimine catalyst is definedby the formula: L(PI)MX₂ where M is a group 4 transition metal selectedfrom Ti, Hf, Zr; PI is a phosphinimine ligand; L is a substituted orunsubstituted cyclopentadienyl type ligand; and X is an activatableligand.

In an embodiment of the invention, the phosphinimine catalyst will havea phosphinimine ligand which is not bridged to, or does not make abridge with another ligand within the metal coordination sphere of thephosphinimine catalyst, such as for example a cyclopentadienyl typeligand.

In an embodiment of the invention, the phosphinimine catalyst will havea cyclopentadienyl type ligand which is not bridged to, or does not makea bridge with another ligand within the metal coordination sphere of thephosphinimine catalyst, such as for example a phosphinimine ligand. Thephosphinimine ligand is defined by the formula: R¹ ₃P═N— wherein each R¹is independently selected from the group consisting of a hydrogen atom;a halogen atom; a C₁₋₂₀ hydrocarbyl radical which is unsubstituted orfurther substituted by one or more halogen atom; a C₁₋₂₀ alkyl radical;a C₁₋₈ alkoxy radical; a C₆₋₁₀ aryl or aryloxy radical; an amidoradical; a silyl radical; and a germanyl radical; P is phosphorus and Nis nitrogen (which bonds to the metal M).

In an embodiment of the invention, the phosphinimine ligand is chosen sothat each R¹ is a hydrocarbyl radical. In a particular embodiment of theinvention, the phosphinimine ligand is tri-(tertiarybutyl)phosphinimine(i.e. where each R¹ is a tertiary butyl group or t-Bu group for short).

As used herein, the term “cyclopentadienyl-type” ligand is meant toinclude ligands which contain at least one five-carbon ring which isbonded to the metal via eta-5 (or in some cases eta-3) bonding. Thus,the term “cyclopentadienyl-type” includes, for example, unsubstitutedcyclopentadienyl, singly or multiply substituted cyclopentadienyl,unsubstituted indenyl, singly or multiply substituted indenyl,unsubstituted fluorenyl and singly or multiply substituted fluorenyl.Hydrogenated versions of indenyl and fluorenyl ligands are alsocontemplated for use, so long as the five-carbon ring which bonds to themetal via eta-5 (or in some cases eta-3) bonding remains intact.Substituents for a cyclopentadienyl ligand, an indenyl ligand (orhydrogenated version thereof) and a fluorenyl ligand (or hydrogenatedversion thereof) may be selected from the group consisting of a C₁₋₃₀hydrocarbyl radical (which hydrocarbyl radical may be unsubstituted orfurther substituted by for example a halide and/or a hydrocarbyl group;for example a suitable substituted C₁₋₃₀ hydrocarbyl radical is apentafluorobenzyl group such as —CH₂C₆F₅); a halogen atom; a C₁₋₈ alkoxyradical; a C₆₋₁₀ aryl or aryloxy radical (each of which may be furthersubstituted by for example a halide and/or a hydrocarbyl group); anamido radical which is unsubstituted or substituted by up to two C₁₋₈alkyl radicals; a phosphido radical which is unsubstituted orsubstituted by up to two C₁₋₈ alkyl radicals; a silyl radical of theformula —Si(R′)₃ wherein each R′ is independently selected from thegroup consisting of hydrogen, a C₁₋₈ alkyl or alkoxy radical, C₆₋₁₀ arylor aryloxy radicals; and a germanyl radical of the formula —Ge(R′)₃wherein R′ is as defined directly above.

The term “perfluorinated aryl group” means that each hydrogen atomattached to a carbon atom in an aryl group has been replaced with afluorine atom as is well understood in the art (e.g. a perfluorinatedphenyl group or substituent has the formula —C₆F₅).

In an embodiment of the invention, the phosphinimine catalyst will havea single or multiply substituted indenyl ligand and a phosphinimineligand which is substituted by three tertiary butyl substituents.

An indenyl ligand (or “Ind” for short) as defined herein will haveframework carbon atoms with the numbering scheme provided below, so thelocation of a substituent can be readily identified.

In an embodiment of the invention, the phosphinimine catalyst will havea singly substituted indenyl ligand and a phosphinimine ligand which issubstituted by three tertiary butyl substituents.

In an embodiment of the invention, the phosphinimine catalyst will havea singly or multiply substituted indenyl ligand where the substituent isselected from the group consisting of a substituted or unsubstitutedalkyl group, a substituted or an unsubstituted aryl group, and asubstituted or unsubstituted benzyl (e.g. C₆H₅CH₂—) group. Suitablesubstituents for the alkyl, aryl or benzyl group may be selected fromthe group consisting of alkyl groups, aryl groups, alkoxy groups,aryloxy groups, alkylaryl groups (e.g. a benzyl group), arylalkyl groupsand halide groups.

In an embodiment of the invention, the phosphinimine catalyst will havea singly substituted indenyl ligand, R²-Indenyl, where the R²substituent is a substituted or unsubstituted alkyl group, a substitutedor an unsubstituted aryl group, or a substituted or unsubstituted benzylgroup. Suitable substituents for an R² alkyl, R² aryl or R² benzyl groupmay be selected from the group consisting of alkyl groups, aryl groups,alkoxy groups, aryloxy groups, alkylaryl groups (e.g. a benzyl group),arylalkyl groups and halide groups.

In an embodiment of the invention, the phosphinimine catalyst will havean indenyl ligand having at least a 1-position substituent (1-R²) wherethe substituent R² is a substituted or unsubstituted alkyl group, asubstituted or an unsubstituted aryl group, or a substituted orunsubstituted benzyl group. Suitable substituents for an R² alkyl, R²aryl or R² benzyl group may be selected from the group consisting ofalkyl groups, aryl groups, alkoxy groups, aryloxy groups, alkylarylgroups (e.g. a benzyl group), arylalkyl groups and halide groups.

In an embodiment of the invention, the phosphinimine catalyst will havea singly substituted indenyl ligand, 1-R²-Indenyl where the substituentR² is in the 1-position of the indenyl ligand and is a substituted orunsubstituted alkyl group, a substituted or unsubstituted aryl group, ora substituted or an unsubstituted benzyl group. Suitable substituentsfor an R² alkyl, R² aryl or R² benzyl group may be selected from thegroup consisting of alkyl groups, aryl groups, alkoxy groups, aryloxygroups, alkylaryl groups (e.g. a benzyl group), arylalkyl groups andhalide groups.

In an embodiment of the invention, the phosphinimine catalyst will havea singly substituted indenyl ligand, 1-R²-Indenyl, where the substituentR² is a (partially/fully) halide substituted alkyl group, a(partially/fully) halide substituted benzyl group, or a(partially/fully) halide substituted aryl group.

In an embodiment of the invention, the phosphinimine catalyst will havea singly substituted indenyl ligand, 1-R²-Indenyl, where the substituentR² is a (partially/fully) halide substituted benzyl group.

When present on an indenyl ligand, a benzyl group can be partially orfully substituted by halide atoms, for example, fluoride atoms. The arylgroup of the benzyl group may be a perfluorinated aryl group, a 2,6(i.e. ortho) fluoro substituted phenyl group, 2,4,6 (i.e. ortho/para)fluoro substituted phenyl group or a 2,3,5,6 (i.e. ortho/meta) fluorosubstituted phenyl group respectively. The benzyl group is, in anembodiment of the invention, located at the 1 position of the indenylligand.

In an embodiment of the invention, the phosphinimine catalyst will havea singly substituted indenyl ligand, 1-R²-Indenyl, where the substituentR² is a pentafluorobenzyl (C₆F₅CH₂—) group.

In an embodiment of the invention, the phosphinimine catalyst has theformula: (1-R²-(Ind))M(N═P(t-Bu)₃)X₂ where R² is a substituted orunsubstituted alkyl group, a substituted or an unsubstituted aryl group,or a substituted or unsubstituted benzyl group, wherein substituents forthe alkyl, aryl or benzyl group are selected from the group consistingof alkyl, aryl, alkoxy, aryloxy, alkylaryl, arylalkyl and halidesubstituents; M is Ti, Zr or Hf; and X is an activatable ligand.

In an embodiment of the invention, the phosphinimine catalyst has theformula: (1-R²-(Ind))M(N═P(t-Bu)₃)X₂ where R² is an alkyl group, an arylgroup or a benzyl group and wherein each of the alkyl group, the arylgroup, and the benzyl group may be unsubstituted or substituted by atleast one fluoride atom; M is Ti, Zr or Hf; and X is an activatableligand.

In an embodiment of the invention, the phosphinimine catalyst has theformula: (1-R²-(Ind))M(N═P(t-Bu)₃)X₂ where R² is an alkyl group, an arylgroup or a benzyl group and wherein each of the alkyl group, the arylgroup, and the benzyl group may be unsubstituted or substituted by atleast one halide atom; M is Ti, Zr or Hf; and X is an activatableligand.

In an embodiment of the invention, the phosphinimine catalyst has theformula: (1-R²-(Ind))Ti(N═P(t-Bu)₃)X₂ where R² is an alkyl group, anaryl group or a benzyl group and wherein each of the alkyl group, thearyl group, and the benzyl group may be unsubstituted or substituted byat least one fluoride atom; and X is an activatable ligand.

In an embodiment of the invention, the phosphinimine catalyst has theformula: (1-C₆F₅CH₂-Ind)M(N═P(t-Bu)₃)X₂, where M is Ti, Zr or Hf; and Xis an activatable ligand.

In an embodiment of the invention, the phosphinimine catalyst has theformula: (1-C₆F₅CH₂-Ind)Ti(N═P(t-Bu)₃)X₂, where X is an activatableligand.

Other organotransition metal catalysts which may also be contemplatedfor use include metallocene catalysts (which have two cyclopentadienyltype ligands), and constrained geometry catalysts (which have an amidotype ligand and a cyclopentadienyl type ligand). Some non-limitingexamples of metallocene catalysts, which may or may not be useful, canbe found in U.S. Pat. Nos. 4,808,561; 4,701,432; 4,937,301; 5,324,800;5,633,394; 4,935,397; 6,002,033 and 6,489,413, which are incorporatedherein by reference. Some non-limiting examples of constrained geometrycatalysts, which may or may not be useful, can be found in U.S. Pat.Nos. 5,057,475; 5,096,867; 5,064,802; 5,132,380; 5,703,187 and6,034,021, all of which are incorporated by reference herein in theirentirety.

The term “activatable”, means that the ligand X may be cleaved from themetal center M via a protonolysis reaction or abstracted from the metalcenter M by suitable acidic or electrophilic catalyst activatorcompounds (also known as “co-catalyst” compounds) respectively, examplesof which are described below. The activatable ligand X may also betransformed into another ligand which is cleaved or abstracted from themetal center M (e.g. a halide may be converted to an alkyl group).Without wishing to be bound by any single theory, protonolysis orabstraction reactions generate an active “cationic” metal center whichcan polymerize olefins.

In embodiments of the present invention, the activatable ligand, X isindependently selected from the group consisting of a hydrogen atom; ahalogen atom, a C₁₋₁₀ hydrocarbyl radical; a C₁₋₁₀ alkoxy radical; and aC₆₋₁₀ aryl or aryloxy radical, where each of the hydrocarbyl, alkoxy,aryl, or aryl oxide radicals may be un-substituted or furthersubstituted by one or more halogen or other group; a C₁₋₈ alkyl; a C₁₋₈alkoxy, a C₈₋₁₀ aryl or aryloxy; an amido or a phosphido radical, butwhere X is not a cyclopentadienyl. Two X ligands may also be joined toone another and form for example, a substituted or unsubstituted dieneligand (i.e. 1,3-butadiene); or a delocalized heteroatom containinggroup such as an acetate or acetamidinate group. In a convenientembodiment of the invention, each X is independently selected from thegroup consisting of a halide atom, a C₁₋₄ alkyl radical and a benzylradical.

Particularly suitable activatable ligands are monoanionic such as ahalide (e.g. chloride) or a hydrocarbyl (e.g. methyl, benzyl).

The catalyst activator (or simply the “activator” for short) used toactivate the transition metal polymerization catalyst can be anysuitable activator including one or more activators selected from thegroup consisting of alkylaluminoxanes and ionic activators, optionallytogether with an alkylating agent.

Without wishing to be bound by theory, alkylaluminoxanes are thought tobe complex aluminum compounds of the formula:

R³ ₂Al¹O(R³Al¹O)_(m)Al¹R³ ₂, wherein each R³ is independently selectedfrom the group consisting of C₁₋₂₀ hydrocarbyl radicals and m is fromabout 3 to about 50. Optionally a hindered phenol can be added to thealkylaluminoxane to provide a molar ratio of Al¹:hindered phenol of fromabout 2:1 to about 5:1 when the hindered phenol is present.

In an embodiment of the invention, R³ of the alkylaluminoxane, is amethyl radical and m is from about 10 to about 40.

The alkylaluminoxanes are typically used in substantial molar excesscompared to the amount of group 4 transition metal in the organometalliccompound/complex. The Al¹:group 4 transition metal molar ratios may befrom about 10:1 to about 10,000:1, or from about 30:1 to about 500:1.

In an embodiment of the invention, the catalyst activator ismethylaluminoxane (MAO).

In an embodiment of the invention, the catalyst activator is modifiedmethylaluminoxane (MMAO).

It is well known in the art, that the alkylaluminoxane can serve dualroles as both an alkylator and an activator. Hence, an alkylaluminoxaneactivator is often used in combination with activatable ligands such ashalogens.

Alternatively, the catalyst activator may be a combination of analkylating agent (which may also serve as a scavenger) with an activatorcapable of ionizing the group 4 of the transition metal catalyst (i.e.an ionic activator). In this context, the activator can be chosen fromone or more alkylaluminoxane and/or an ionic activator, since analkylaluminoxane may serve as both an activator and an alkylating agent.

When present, the alkylating agent may be selected from the groupconsisting of (R⁴)_(p)MgX² _(2-p), wherein X² is a halide and each R⁴ isindependently selected from the group consisting of C₁₋₁₀ alkyl radicalsand p is 1 or 2; R⁴Li wherein in R⁴ is as defined above, (R⁴)_(q)ZnX²_(2-q) wherein R⁴ is as defined above, X² is halogen and q is 1 or 2;(R⁴)_(s) Al²X² _(3-s) wherein R⁴ is as defined above, X² is halogen ands is an integer from 1 to 3. In some embodiments, in the above compoundsR⁴ is a C₁₋₄ alkyl radical, and X² is chlorine. Commercially availablecompounds include triethyl aluminum (TEAL), diethyl aluminum chloride(DEAC), dibutyl magnesium ((Bu)₂Mg), and butyl ethyl magnesium (BuEtMgor BuMgEt). Alkylaluminoxanes can also be used as alkylating agents.

The ionic activator may be selected from the group consisting of: (i)compounds of the formula [R⁵]⁺[B(R⁶)₄]⁻ wherein B is a boron atom, R⁵ isa cyclic C₅₋₇ aromatic cation or a triphenyl methyl cation and each R⁶is independently selected from the group consisting of phenyl radicalswhich are unsubstituted or substituted with from 3 to 5 substituentsselected from the group consisting of a fluorine atom, a C₁₋₄ alkyl oralkoxy radical which is unsubstituted or substituted by a fluorine atom;and a silyl radical of the formula —Si—(R⁷)₃; wherein each R⁷ isindependently selected from the group consisting of a hydrogen atom anda C₁₋₄ alkyl radical; and (ii) compounds of the formula [(R⁸)_(t)ZH]⁺[B(R⁶)₄]⁻ wherein B is a boron atom, H is a hydrogen atom, Z is anitrogen atom or phosphorus atom, t is 2 or 3 and R⁸ is selected fromthe group consisting of C₁₋₈ alkyl radicals, a phenyl radical which isunsubstituted or substituted by up to three C₁₋₄ alkyl radicals, or oneR⁸ taken together with the nitrogen atom may form an anilinium radicaland R⁶ is as defined above; and (iii) compounds of the formula B(R⁶)₃wherein R⁶ is as defined above.

In the above compounds R⁶ is a pentafluorophenyl radical, and R⁵ is atriphenylmethyl cation, Z is a nitrogen atom and R⁸ is a C₁₋₄ alkylradical or R⁸ taken together with the nitrogen atom forms an aniliniumradical which is substituted by two C₁₋₄ alkyl radicals.

Examples of compounds capable of ionizing the transition metal catalystinclude the following compounds: triethylammonium tetra(phenyl)boron,tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammoniumtetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron,trimethylammonium tetra(o-tolyl)boron, tributylammoniumtetra(pentafluorophenyl)boron, tripropylammoniumtetra(o,p-dimethylphenyl)boron, tributylammoniumtetra(m,m-dimethylphenyl)boron, tributylammoniumtetra(p-trifluoromethylphenyl)boron, tributylammoniumtetra(pentafluorophenyl)boron, tri(n-butyl)ammonium tetra(o-tolyl)boron,N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylaniliniumtetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)_(n)-butylboron,N,N-2,4,6-pentamethylanilinium tetra(phenyl)boron,di-(isopropyl)ammonium tetra(pentafluorophenyl)boron,dicyclohexylammonium tetra(phenyl)boron, triphenylphosphoniumtetra)phenyl)boron, tri(methylphenyl)phosphonium tetra(phenyl)boron,tri(dimethylphenyl)phosphonium tetra(phenyl)boron, tropilliumtetrakispentafluorophenyl borate, triphenylmethyliumtetrakispentafluorophenyl borate, benzene(diazonium)tetrakispentafluorophenyl borate, tropilliumphenyltris-pentafluorophenyl borate, triphenylmethyliumphenyl-trispentafluorophenyl borate, benzene (diazonium)phenyltrispentafluorophenyl borate, tropilliumtetrakis(2,3,5,6-tetrafluorophenyl)borate, triphenylmethyliumtetrakis(2,3,5,6-tetrafluorophenyl)borate, benzene(diazonium)tetrakis(3,4,5-trifluorophenyl)borate, tropilliumtetrakis(3,4,5-trifluorophenyl)borate, benzene(diazonium)tetrakis(3,4,5-trifluorophenyl)borate, tropilliumtetrakis(1,2,2-trifluoroethenyl)borate, trophenylmethyliumtetrakis(1,2,2-trifluoroethenyl)borate,benzene(diazonium)tetrakis(1,2,2-trifluoroethenyl)borate, tropilliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, triphenylmethyliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, and benzene(diazonium)tetrakis(2,3,4,5-tetrafluorophenyl) borate.

Commercially available activators which are capable of ionizing thetransition metal catalyst include:

N,N-dimethylaniliniumtetrakispentafluorophenyl borate(“[Me₂NHPh][B(C₆F₅)₄]”); triphenylmethylium tetrakispentafluorophenylborate (“[Ph₃C][B(C₆F₅)₄]”); and trispentafluorophenyl boron.

In an embodiment of the invention, the ionic activator compounds may beused in amounts which provide a molar ratio of group 4 transition metalto boron that will be from about 1:1 to about 1:6.

Optionally, mixtures of alkylaluminoxanes and ionic activators can beused as activators for the organometallic complex.

In some embodiments of the current invention, the polymerizationcatalyst system may comprise an inert support (note: the terms “support”and “inert support” are used interchangeably herein). In one embodimentof the invention, the polymerization catalyst system comprises aphosphinimine catalyst which is supported on an inert support.

The inert support can be any support known in the art to be suitable foruse with polymerization catalysts. For example the support can be anyporous or non-porous support material, such as talc, inorganic oxides,inorganic chlorides, aluminophosphates (i.e. AlPO₄) and polymer supports(e.g. polystyrene, etc). Hence, supports include Group 2, 3, 4, 5, 13and 14 metal oxides generally, such as silica, alumina, silica-alumina,magnesium oxide, magnesium chloride, zirconia, titania, clay (e.g.montmorillonite) and mixtures thereof.

Agglomerate supports such as agglomerates of silica and clay may also beused as a support.

Supports are generally used in calcined form. An inorganic oxidesupport, for example, will contain acidic surface hydroxyl groups whichwill react with a polymerization catalyst. Prior to use, the inorganicoxide may be dehydrated to remove water and to reduce the concentrationof surface hydroxyl groups. Calcination or dehydration of a support iswell known in the art. In an embodiment of the invention, the support iscalcined at temperatures above about 200° C., or above about 300° C., orabove about 400° C., or above about 500° C. In other embodiments, thesupport is calcined at from about 500° C. to about 1000° C., or fromabout 600° C. to about 900° C. The resulting support may be free ofadsorbed water and may have a surface hydroxyl content from about 0.1 toabout 5 mmol/g of support, or from about 0.5 to about 3 mmol/g. Theamount of hydroxyl groups in a silica support may be determinedaccording to the method disclosed by J. B. Peri and A. L. Hensley Jr.,in J. Phys. Chem., 72 (8), 1968, pg 2926.

The support material, especially an inorganic oxide, typically has asurface area of from about 10 to about 700 m²/g, a pore volume in therange from about 0.1 to about 4.0 cc/g and an average particle size offrom about 5 to about 500 μm. In a more specific embodiment, the supportmaterial has a surface area of from about 50 to about 500 m²/g, a porevolume in the range from about 0.5 to about 3.5 cc/g and an averageparticle size of from about 10 to about 200 μm. In another more specificembodiment the support material has a surface area of from about 100 toabout 400 m²/g, a pore volume in the range from about 0.8 to about 3.0cc/g and an average particle size of from about 5 to about 100 μm.

The support material, especially an inorganic oxide, typically has anaverage pore size (i.e. pore diameter) of from about 10 to about 1000Angstroms (Å). In a more specific embodiment, the support material hasan average pore size of from about 50 to about 500A. In another morespecific embodiment, the support material has an average pore size offrom about 75 to about 350A.

The surface area and pore volume of a support may be determined bynitrogen adsorption according to B.E.T. techniques, which are well knownin the art and are described in the Journal of the American ChemicalSociety, 1938, v 60, pg 309-319.

A suitable silica support has a high surface area and is amorphous. Byway of example only, useful silicas are commercially available under thetrademark of Sylopol® 958, 955 and 2408 by the Davison Catalysts, aDivision of W. R. Grace and Company and ES-70W by Ineos Silica.

Agglomerate supports comprising a clay mineral and an inorganic oxide,may be prepared using a number techniques well known in the artincluding pelletizing, extrusion, drying or precipitation, spray-drying,shaping into beads in a rotating coating drum, and the like. Anodulization technique may also be used. Methods to make agglomeratesupports comprising a clay mineral and an inorganic oxide includespray-drying a slurry of a clay mineral and an inorganic oxide. Methodsto make agglomerate supports comprising a clay mineral and an inorganicoxide are disclosed in U.S. Pat. Nos. 6,686,306; 6,399,535; 6,734,131;6,559,090 and 6,958,375.

An agglomerate of clay and inorganic oxide may have the followingproperties: a surface area of from about 20 to about 800 m²/g, or fromabout 50 to about 600 m²/g; particles with a bulk density of from about0.15 to about 1 g/ml, or from about 0.20 to about 0.75 g/ml; an averagepore diameter of from about 30 to about 300 Angstroms (Å), or from about60 to about 150 Å; a total pore volume of from about 0.10 to about 2.0cc/g, or from about 0.5 to about 1.8 cc/g; and an average particle sizeof from about 4 to about 250 microns (μm), or from about 8 to about 100microns.

Alternatively, a support, for example a silica support, may be treatedwith one or more salts of the type: Zr(SO₄)₂.4H₂O, ZrO(NO₃)₂, andFe(NO₃)₃ as taught in co-pending Canadian Patent Application No.2,716,772. Supports that have been otherwise chemically treated are alsocontemplated for use with the catalysts and processes described herein.

The present invention is not limited to any particular procedure forsupporting a transition metal catalyst or catalyst system components.Processes for depositing such catalysts (e.g. a phosphinimine catalyst)as well as a catalyst activator on a support are well known in the art(for some non-limiting examples of catalyst supporting methods, see“Supported Catalysts” by James H. Clark and Duncan J. Macquarrie,published online Nov. 15, 2002 in the Kirk-Othmer Encyclopedia ofChemical Technology Copyright @ 2001 by John Wiley & Sons, Inc.; forsome non-limiting methods to support an organotransition metal catalystsee U.S. Pat. No. 5,965,677). For example, a transition metal catalyst(e.g. a phosphinimine catalyst) may be added to a support byco-precipitation with the support material. The activator can be addedto the support before and/or after the transition metal catalyst ortogether with the transition metal catalyst. Optionally, the activatorcan be added to a supported transition metal catalyst in situ or atransition metal catalyst may be added to the support in situ or atransition metal catalyst can be added to a supported activator in situ.A transition metal catalyst may be slurried or dissolved in a suitablediluent or solvent and then added to the support. Suitable solvents ordiluents include but are not limited to hydrocarbons and mineral oil. Atransition metal catalyst for example, may be added to the solidsupport, in the form of a solid, solution or slurry, followed by theaddition of the activator in solid form or as a solution or slurry.Transition metal catalyst (e.g. phosphinimine catalyst), catalystactivator, and support can be mixed together in the presence or absenceof a solvent.

Polymerization Process

Copolymer compositions can be made using a single reactor, for example,a single gas phase or slurry phase reactor. A polymerization catalystsystem comprising a single transition metal catalyst in a single gasphase reactor may be used.

Detailed descriptions of slurry polymerization processes are widelyreported in the patent literature. For example, particle formpolymerization, or a slurry process where the temperature is kept belowthe temperature at which the polymer goes into solution is described inU.S. Pat. No. 3,248,179. Other slurry processes include those employinga loop reactor and those utilizing a plurality of stirred reactors inseries, parallel, or combinations thereof. Non-limiting examples ofslurry processes include continuous loop or stirred tank processes.Further examples of slurry processes are described in U.S. Pat. No.4,613,484.

Slurry processes are conducted in the presence of a hydrocarbon diluentsuch as an alkane (including isoalkanes), an aromatic or a cycloalkane.The diluent may also be the alpha olefin comonomer used incopolymerizations. Alkane diluents include propane, butanes, (i.e.normal butane and/or isobutane), pentanes, hexanes, heptanes andoctanes. The monomers may be soluble in (or miscible with) the diluent,but the polymer is not (under polymerization conditions). Thepolymerization temperature may be from about 5° C. to about 200° C., orless than about 120° C. typically from about 10° C. to about 100° C. Thereaction temperature is selected so that the ethylene copolymer isproduced in the form of solid particles. The reaction pressure isinfluenced by the choice of diluent and reaction temperature. Forexample, pressures may range from about 15 to about 45 atmospheres(about 220 to about 660 psi or about 1500 to about 4600 kPa) whenisobutane is used as diluent (see, for example, U.S. Pat. No. 4,325,849)to approximately twice that (i.e. from about 30 to about 90atmospheres-about 440 to about 1300 psi or about 3000-9100 kPa) whenpropane is used (see U.S. Pat. No. 5,684,097). The pressure in a slurryprocess is kept sufficiently high to keep at least part of the ethylenemonomer in the liquid phase. The reaction typically takes place in ajacketed closed loop reactor having an internal stirrer (e.g. animpeller) and at least one settling leg. Catalyst, monomers and diluentsare fed to the reactor as liquids or suspensions. The slurry circulatesthrough the reactor and the jacket is used to control the temperature ofthe reactor. Through a series of let-down valves the slurry enters asettling leg and then is let down in pressure to flash the diluent andunreacted monomers and recover the polymer generally in a cyclone. Thediluent and unreacted monomers are recovered and recycled back to thereactor.

A gas phase polymerization process is commonly carried out in afluidized bed reactor. Such gas phase processes are widely described inthe literature (see for example U.S. Pat. Nos. 4,543,399, 4,588,790,5,028,670, 5,317,036, 5,352,749, 5,405,922, 5,436,304, 5,453,471,5,462,999, 5,616,661 and 5,668,228). In general, a fluidized bed gasphase polymerization reactor employs a “bed” of polymer and catalystwhich is fluidized by a flow of monomer, comonomer and other optionalcomponents which are at least partially gaseous. Heat is generated bythe enthalpy of polymerization of the monomer (and comonomers) flowingthrough the bed. Un-reacted monomer, comonomer and other optionalgaseous components exit the fluidized bed and are contacted with acooling system to remove this heat. The cooled gas stream, includingmonomer, comonomer and optional other components (such as condensableliquids), is then re-circulated through the polymerization zone,together with “make-up” monomer (and comonomer) to replace that whichwas polymerized on the previous pass. Simultaneously, polymer product iswithdrawn from the reactor. As will be appreciated by those skilled inthe art, the “fluidized” nature of the polymerization bed helps toevenly distribute/mix the heat of reaction and thereby minimize theformation of localized temperature gradients.

The reactor pressure in a gas phase process may vary from aboutatmospheric to about 600 psig. In a more specific embodiment, thepressure can range from about 100 psig (about 690 kPa) to about 500 psig(about 3448 kPa). In another more specific embodiment, the pressure canrange from about 200 psig (about 1379 kPa) to about 400 psig (about 2759kPa). In yet another more specific embodiment, the pressure can rangefrom about 250 psig (about 1724 kPa) to about 350 psig (about 2414 kPa).

The reactor temperature in a gas phase process may vary according to theheat of polymerization as described above. In a specific embodiment, thereactor temperature can be from about 30° C. to about 130° C. In anotherspecific embodiment, the reactor temperature can be from about 60° C. toabout 120° C. In yet another specific embodiment, the reactortemperature can be from about 70° C. to about 110° C. In still yetanother specific embodiment, the temperature of a gas phase process canbe from about 70° C. to about 100° C.

The fluidized bed process described above is well adapted for thepreparation of polyethylene but other monomers (i.e. comonomers) mayalso be employed. Monomers and comonomers include ethylene and C₃₋₁₂alpha olefins respectively, where C₃₋₁₂ alpha olefins are unsubstitutedor substituted by up to two C₁₋₆ alkyl radicals, C₈₋₁₂ vinyl aromaticmonomers which are unsubstituted or substituted by up to twosubstituents selected from the group consisting of C₁₋₄ alkyl radicals,C₄₋₁₂ straight chained or cyclic diolefins which are unsubstituted orsubstituted by a C₁₋₄ alkyl radical. Illustrative non-limiting examplesof such alpha-olefins are one or more of propylene, 1-butene, 1-pentene,1-hexene, 1-octene, and 1-decene, styrene, alpha methyl styrene,p-tert-butyl styrene, and the constrained-ring cyclic olefins such ascyclobutene, cyclopentene, dicyclopentadiene norbornene,alkyl-substituted norbornenes, alkenyl-substituted norbornenes and thelike (e.g. 5-methylene-2-norbornene and 5-ethylidene-2-norbornene,bicyclo-(2,2,1)-hepta-2,5-diene).

In one embodiment, the invention is directed toward a polymerizationprocess involving the polymerization of ethylene with one or more ofcomonomer(s) including linear or branched comonomer(s) having from 3 to30 carbon atoms, or 3-12 carbon atoms, or 3 to 8 carbon atoms.

The process is particularly well suited to the copolymerizationreactions involving the polymerization of ethylene in combination withone or more of the comonomers, for example alpha-olefin comonomers suchas propylene, butene-1, pentene-1,4-methylpentene-1, hexene-1, octene-1,decene-1, styrene and cyclic and polycyclic olefins such ascyclopentene, norbornene and cyclohexene or a combination thereof. Othercomonomers for use with ethylene can include polar vinyl monomers,diolefins such as 1,3-butadiene, 1,4-pentadiene, 1,4-hexadiene,1,5-hexadiene, norbornadiene, and other unsaturated monomers includingacetylene and aldehyde monomers. Higher alpha-olefins and polyenes ormacromers can be used also.

The comonomer is an alpha-olefin having from 3 to 15 carbon atoms, orfrom 4 to 12 carbon atoms, or from 4 to 10 carbon atoms.

In an embodiment of the invention, ethylene comprises at least about 75wt % of the total weight of monomer (i.e. ethylene) and comonomer (i.e.alpha olefin) that is fed to a polymerization reactor.

In an embodiment of the invention, ethylene comprises at least about 85wt % of the total weight of monomer (i.e. ethylene) and comonomer (i.e.alpha olefin) that is fed to a polymerization reactor.

In an embodiment of the invention, ethylene is polymerized with at leasttwo different comonomers to form a terpolymer and the like. Examples ofcomonomers are a combination of monomers, such as, alpha-olefin monomershaving 3 to 10 carbon atoms, or 3 to 8 carbon atoms, optionally with atleast one diene monomer. Example terpolymers include combinations suchas ethylene/butene-1/hexene-1, ethylene/propylene/butene-1,ethylene/propylene/hexene-1, ethylene/propylene/norbornadiene,ethylene/propylene/1,4-hexadiene and the like.

In an embodiment of the invention, a copolymer of ethylene and analpha-olefin having from 3-8 carbon atoms is made in a single reactor inthe presence of a polymerization catalyst system comprising a singlegroup 4 organotransition metal catalyst.

In an embodiment of the invention, a copolymer of ethylene and analpha-olefin having from 3-8 carbon atoms is made in a single gas phasereactor in the presence of a polymerization catalyst system comprising asingle group 4 organotransition metal catalyst.

In an embodiment of the invention, a copolymer of ethylene and analpha-olefin having from 3-8 carbon atoms is made in a single reactor inthe presence of a polymerization catalyst system comprising a singlegroup 4 organotransition metal catalyst; a catalyst activator; and asupport.

In an embodiment of the invention, a copolymer of ethylene and analpha-olefin having from 3-8 carbon atoms is made in a single gas phasereactor in the presence of a polymerization catalyst system comprising asingle group 4 organotransition metal catalyst; a catalyst activator;and a support.

In an embodiment of the invention, a copolymer of ethylene and analpha-olefin having from 3-8 carbon atoms is made in a single gas phasereactor in the presence of a polymerization catalyst system comprising asingle transition metal catalyst, where the single transition metalcatalyst is a group 4 phosphinimine catalyst.

In an embodiment of the invention, a copolymer of ethylene and analpha-olefin having from 3-8 carbon atoms is made in a single gas phasereactor in the presence of a polymerization catalyst system comprising asingle transition metal catalyst, where the single transition metalcatalyst is a group 4 phosphinimine catalyst having the formula:

(1-R²-Indenyl)Ti(N═P(t-Bu)₃)X₂;

wherein R² is a substituted or unsubstituted alkyl group, a substitutedor an unsubstituted aryl group, or a substituted or unsubstituted benzylgroup, wherein substituents for the alkyl, aryl or benzyl group areselected from the group consisting of alkyl, aryl, alkoxy, aryloxy,alkylaryl, arylalkyl and halide substituents; and wherein X is anactivatable ligand.

In an embodiment of the invention, a copolymer of ethylene and analpha-olefin having from 3-8 carbon atoms is made in a single gas phasereactor with a polymerization catalyst system comprising: aphosphinimine catalyst; an alkylaluminoxane cocatalyst; and a support.

In an embodiment of the invention, a copolymer of ethylene and analpha-olefin having from 3-8 carbon atoms is made in a single gas phasereactor with a polymerization catalyst system comprising: aphosphinimine catalyst; an alkylaluminoxane cocatalyst; a support; and acatalyst modifier (which is further described below).

In an embodiment of the invention, a copolymer of ethylene and analpha-olefin having from 3-8 carbon atoms is made in a single reactorwith a polymerization catalyst system comprising: a phosphiniminecatalyst having the formula (1-R²-Ind)Ti(N═P(t-Bu)₃)X₂ where R² is analkyl group, an aryl group or a benzyl group wherein each of the alkylgroup, the aryl group, or the benzyl group may be unsubstituted orsubstituted by at least one halide atom, and where X is an activatableligand; and an activator.

In an embodiment of the invention, a copolymer of ethylene and analpha-olefin having from 3-8 carbon atoms is made in a single gas phasereactor with a polymerization catalyst system comprising: aphosphinimine catalyst having the formula (1-R²-Ind)Ti(N═P(t-Bu)₃)X₂where R² is an alkyl group, an aryl group or a benzyl group wherein eachof the alkyl group, the aryl group, or the benzyl group may beunsubstituted or substituted by at least one halide atom, where X is anactivatable ligand; an activator; and an inert support.

In an embodiment of the invention, a copolymer of ethylene and analpha-olefin having from 3-8 carbon atoms is made in a single gas phasereactor with a polymerization catalyst system comprising: aphosphinimine catalyst having the formula (1-R²-Ind)Ti(N═P(t-Bu)₃)X₂where R² is an alkyl group, an aryl group or a benzyl group wherein eachof the alkyl group, the aryl group, or the benzyl group may beunsubstituted or substituted by at least one halide atom, where X is anactivatable ligand; an activator; an inert support; and a catalystmodifier.

In an embodiment of the invention, the copolymer is a copolymer ofethylene and an alpha-olefin having from 3-8 carbon atoms, and is madein a single gas phase reactor with a polymerization catalyst systemcomprising: a phosphinimine catalyst having the formula(1-C₆F₅CH₂-Ind)Ti(N═P(t-Bu)₃)X₂ where X is an activatable ligand; anactivator; and an inert support.

In an embodiment of the invention, the copolymer is a copolymer ofethylene and an alpha-olefin having from 3-8 carbon atoms, and is madein a single gas phase reactor with a polymerization catalyst systemcomprising: a phosphinimine catalyst having the formula(1-C₆F₅CH₂-Ind)Ti(N═P(t-Bu)₃)X₂ where X is an activatable ligand; anactivator; an inert support; and a catalyst modifier.

In an embodiment of the invention, an olefin polymerization processgives an ethylene copolymer, the process comprising contacting ethyleneand at least one alpha olefin having from 3-8 carbon atoms with apolymerization catalyst system in a single gas phase reactor; whereinthe polymerization catalyst system comprises a single transition metalcatalyst, a support, and a catalyst activator; and wherein the singletransition metal catalyst is a group 4 organotransition metal catalyst.

In an embodiment of the invention, an olefin polymerization processgives an ethylene copolymer, the process comprising contacting ethyleneand at least one alpha olefin having from 3-8 carbon atoms with apolymerization catalyst system in a single gas phase reactor; whereinthe polymerization catalyst system comprises a single transition metalcatalyst, a support, a catalyst activator, and a catalyst modifier; andwherein the single transition metal catalyst is a group 4organotransition metal catalyst.

In an embodiment of the invention, an olefin polymerization processgives an ethylene copolymer, the process comprising contacting ethyleneand at least one alpha olefin having from 3-8 carbon atoms with apolymerization catalyst system in a single gas phase reactor; whereinthe polymerization catalyst system comprises a single transition metalcatalyst, a support, and a catalyst activator; and wherein the singletransition metal catalyst is a group 4 phosphinimine catalyst.

In an embodiment of the invention, an olefin polymerization processgives an ethylene copolymer, the process comprising contacting ethyleneand at least one alpha olefin having from 3-8 carbon atoms with apolymerization catalyst system in a single gas phase reactor; whereinthe polymerization catalyst system comprises a single transition metalcatalyst, a support, a catalyst activator, and a catalyst modifier; andwherein the single transition metal catalyst is a group 4 phosphiniminecatalyst.

In an embodiment of the invention, an olefin polymerization processgives an ethylene copolymer, the process comprising contacting ethyleneand at least one alpha olefin having from 3-8 carbon atoms with apolymerization catalyst system in a single gas phase reactor; whereinthe polymerization catalyst system comprises a single transition metalcatalyst, a support, a catalyst activator, and a catalyst modifier; andwherein the single transition metal catalyst is a group 4 phosphiniminecatalyst having the formula: (1-R²-Indenyl)Ti(N═P(t-Bu)₃)X₂; wherein R²is a substituted or unsubstituted alkyl group, a substituted or anunsubstituted aryl group, or a substituted or unsubstituted benzylgroup, wherein substituents for the alkyl, aryl or benzyl group areselected from the group consisting of alkyl, aryl, alkoxy, aryloxy,alkylaryl, arylalkyl and halide substituents; and wherein X is anactivatable ligand.

The polymerization catalyst system may be fed to a reactor system in anumber of ways. If the transition metal catalyst is supported on asuitable support, the transition metal catalyst may be fed to a reactorin dry mode using a dry catalyst feeder, examples of which are wellknown in the art. Alternatively, a supported transition metal catalystmay be fed to a reactor as a slurry in a suitable diluent. If thetransition metal catalyst is unsupported, the catalyst can be fed to areactor as a solution or as a slurry in a suitable solvent or diluents.Polymerization catalyst system components, which may include atransition metal catalyst, an activator, a scavenger, an inert support,and a catalyst modifier, may be combined prior to their addition to apolymerization zone, or they may be combined on route to apolymerization zone. To combine polymerization catalyst systemcomponents on route to a polymerization zone they can be fed assolutions or slurries (in suitable solvents or diluents) using variousfeed line configurations which may become coterminous before reachingthe reactor. Such configurations can be designed to provide areas inwhich catalyst system components flowing to a reactor can mix and reactwith one another over various “hold up” times which can be moderated bychanging the solution or slurry flow rates of the catalyst systemcomponents.

Catalyst Modifier

A “catalyst modifier” is a compound which, when added to apolymerization catalyst system or used in the presence of the same inappropriate amounts, can reduce, prevent or mitigate at least one: offouling, sheeting, temperature excursions, and static level of amaterial in polymerization reactor; can alter catalyst kinetics; and/orcan alter the properties of copolymer product obtained in apolymerization process.

A long chain amine type catalyst modifier may be added to a reactor zone(or associated process equipment) separately from the polymerizationcatalyst system, as part of the polymerization catalyst system, or bothas described in co-pending CA Pat. Appl. No. 2,742,461. The long chainamine can be a long chain substituted monoalkanolamine, or a long chainsubstituted dialkanolamine as described in co-pending CA Pat. Appl. No.2,742,461, which is incorporated herein in full.

In an embodiment of the invention, the catalyst modifier employedcomprises at least one long chain amine compound represented by theformula: R⁹R¹⁰ _(x)N((CH₂)_(n)OH)_(y) where R⁹ is a hydrocarbyl grouphaving from 5 to 30 carbon atoms, R¹⁹ is hydrogen or a hydrocarbyl grouphaving from 1 to 30 carbon atoms, x is 1 or 0, y is 1 when x is 1, y is2 when x is 0, each n is independently an integer from 1 to 30 when y is2, and n is an integer from 1 to 30 when y is 1.

In an embodiment of the invention, the catalyst modifier comprises atleast one long chain substituted monoalkanolamine represented by theformula R⁹R¹⁰N((CH₂)_(n)OH) where R⁹ is a hydrocarbyl group havinganywhere from 5 to 30 carbon atoms, R¹⁰ is a hydrogen or a hydrocarbylgroup having anywhere from 1 to 30 carbon atoms, and n is an integerfrom 1-20.

In an embodiment of the invention, the catalyst modifier comprises atleast one long chain substituted dialkanolamine represented by theformula: R⁹N((CH₂)_(n)OH)((CH₂)_(m)OH) where R⁹ is a hydrocarbyl grouphaving anywhere from 5 to 30 carbon atoms, and n and m are integers from1-20.

In an embodiment of the invention, the catalyst modifier comprises atleast one long chain substituted dialkanolamine represented by theformula: R⁹N((CH₂)_(x)OH)₂ where R⁹ is a hydrocarbyl group havinganywhere from 6 to 30 carbon atoms, and x is an integer from 1-20.

In an embodiment of the invention, the catalyst modifier comprises atleast one long chain substituted dialkanolamine represented by theformula: R⁹N((CH₂)_(x)OH)₂ where R⁹ is a hydrocarbyl group havinganywhere from 6 to 30 carbon atoms, and x is 2 or 3.

In an embodiment of the invention, the catalyst modifier comprises atleast one long chain substituted dialkanolamine represented by theformula: R⁹N((CH₂)_(x)OH)₂ where R⁹ is a linear hydrocarbyl group havinganywhere from 6 to 30 carbon atoms, and x is 2 or 3.

In an embodiment of the invention, the catalyst modifier comprises atleast one long chain substituted dialkanolamine represented by theformula: R⁹N(CH₂CH₂OH)₂ where R⁹ is a linear hydrocarbyl group havinganywhere from 6 to 30 carbon atoms.

In an embodiment of the invention, the catalyst modifier comprises atleast one long chain substituted dialkanolamine represented by theformula: R⁹N(CH₂CH₂OH)₂ where R⁹ is a linear, saturated alkyl grouphaving anywhere from 6 to 30 carbon atoms.

In an embodiment of the invention, the catalyst modifier comprises atleast one long chain substituted dialkanolamine represented by theformula: R⁹N(CH₂CH₂OH)₂ where R⁹ is a hydrocarbyl group having anywherefrom 8 to 22 carbon atoms.

In an embodiment of the invention, the catalyst modifier comprises along chain substituted dialkanolamine represented by the formula:C₁₈H₃₇N(CH₂CH₂OH)₂.

In an embodiment of the invention, the catalyst modifier comprises longchain substituted dialkanolamines represented by the formulas:C₁₃H₂₇N(CH₂CH₂OH)₂ and C₁₅H₃₁N(CH₂CH₂OH)₂.

In an embodiment of the invention, the catalyst modifier comprises amixture of long chain substituted dialkanolamines represented by theformula: R⁹N(CH₂CH₂OH)₂ where R⁹ is a hydrocarbyl group having anywherefrom 8 to 18 carbon atoms.

Non limiting examples of catalyst modifiers which can be used areKemamine AS990™, Kemamine AS-650™, Armostat-1800™,bis-hydroxy-cocoamine, 2,2′-octadecyl-amino-bisethanol, and Atmer-163™.

The amount of catalyst modifier added to a reactor (or other associatedprocess equipment) is conveniently represented herein as the parts permillion (ppm) of catalyst modifier based on the weight of copolymerproduced.

The amount of catalyst modifier included in a polymerization catalystsystem is conveniently represented herein as a weight percent (wt %) ofthe catalyst modifier based on the total weight of the polymerizationcatalyst system (e.g. the combined weight of the transition metalcatalyst, the inert support, the cocatalyst and the catalyst modifier).

The catalyst modifier may be added to a polymerization reactor in anumber of ways. The catalyst modifier may be added to a reactor systemseparately from the polymerization catalyst system or it may be combinedwith the polymerization catalyst system prior to feeding the combinationto a reactor system.

If the catalyst modifier is added to the polymerization catalyst systemprior to its addition to a reactor, then the catalyst modifier can beadded at any point during the preparation of the polymerization catalystsystem. Thus, one transition metal catalyst, at least one activator, atleast one inert support and at least one catalyst modifier may becombined in any order to form a polymerization catalyst system suitablefor use. In specific embodiments of the invention: the catalyst modifiermay be added to a support after both the transition metal catalyst andthe cocatalyst have been added; the catalyst modifier may be added to asupport before either of the transition metal catalyst or the cocatalystare added; the catalyst modifier may be added to a support after thetransition metal catalyst but before the cocatalyst; the catalystmodifier may be added to a support after the cocatalyst but before thetransition metal catalyst. Also, the catalyst modifier can be added inportions during any stage of the preparation of the polymerizationcatalyst system.

The catalyst modifier may be included in the polymerization catalystsystem (or where appropriate, added to a polymerization catalyst systemcomponent or components which may comprise one transition metalcatalyst, the inert support and the cocatalyst) in any suitable manner.By way of non-limiting example, the catalyst modifier may be dry blended(if it is a solid) with the polymerization catalyst system (or apolymerization catalyst system component) or it may be added neat (ifthe catalyst modifier is a liquid) or it may be added as solution orslurry in a suitable hydrocarbon solvent or diluent respectively. Thepolymerization catalyst system (or polymerization catalyst systemcomponents) can likewise be put into solution or made into a slurryusing suitable solvents or diluents respectively, followed by additionof the catalyst modifier (as a neat solid or liquid or as a solution ora slurry in suitable solvents or diluents) or vice versa. Alternatively,the catalyst modifier may be deposited onto a separate support and theresulting supported catalyst modifier blended either dry or in a slurrywith the polymerization catalyst system (or a polymerization catalystsystem component).

In an embodiment of the present invention, the catalyst modifier isadded to a polymerization catalyst system already comprising the singletransition metal catalyst, inert support and cocatalyst. The catalystmodifier can be added to the polymerization catalyst system offline andprior to addition of the polymerization catalyst system to thepolymerization zone, or the catalyst modifier may be added to thepolymerization catalyst system, or components on route to apolymerization reactor.

The catalyst modifier may be fed to a reactor system using anyappropriate method known to persons skilled in the art. For example, thecatalyst modifier may be fed to a reactor system as a solution or as aslurry in a suitable solvent or diluent respectively. Suitable solventsor diluents are inert hydrocarbons well known to persons skilled in theart and generally include aromatics, paraffins, and cycloparaffinicssuch as for example benzene, toluene, xylene, cyclohexane, fuel oil,isobutane, mineral oil, kerosene and the like. Further specific examplesinclude but are not limited to hexane, heptanes, isopentane and mixturesthereof. Alternatively, the catalyst modifier may be added to an inertsupport material and then fed to a polymerization reactor as a dry feedor a slurry feed. The catalyst modifier may be fed to various locationsin a reactor system. When considering a fluidized bed process forexample, the catalyst modifier may be fed directly to any area of thereaction zone (for example, when added as a solution), or any area ofthe entrainment zone, or it may be fed to any area within the recycleloop, where such areas are found to be effective sites at which to feeda catalyst modifier.

When added as a solution or mixture with a solvent or diluentrespectively, the catalyst modifier may make up, for example, from about0.1 to about 30 wt % of the solution or mixture, or from about 0.1 toabout 20 wt %, or from about 0.1 to about 10 wt %, or from about 0.1 toabout 5 wt % or from about 0.1 to about 2.5 wt % or from about 0.2 toabout 2.0 wt %, although a person skilled in the art will recognize thatfurther, possibly broader ranges, may also be used and so someembodiments of the invention should not be limited in this regard.

The catalyst modifier can be added to a reactor with all or a portion ofone or more of the monomers or the cycle gas.

The catalyst modifier can be added to a reactor through a dedicated feedline or added to any convenient feed stream including an ethylene feedstream, a comonomer feed stream, a catalyst feed line or a recycle line.

The catalyst modifier can be fed to a location in a fluidized bed systemin a continuous or intermittent manner.

In an embodiment of the invention, the rate of addition of a catalystmodifier to a reactor will be programmed using measured reactor staticlevels (or other lead indicators such as reactor temperature) asprogramming inputs, so as to maintain a constant or pre-determined levelof static (or for example, temperature) in a polymerization reactor.

The catalyst modifier can be added to a reactor at a time before, afteror during the start of the polymerization reaction.

The catalyst modifier may be added to the polymerization catalyst systemor to one or more polymerization catalyst system components (e.g. aphosphinimine catalyst, inert support, or cocatalyst) on route to areaction zone.

In an embodiment of the invention, the catalyst modifier is addeddirectly to a reaction zone, separately from the polymerization catalystsystem. Most typically, it is so added by spraying a solution or mixtureof the catalyst modifier directly into a reaction zone.

In an embodiment of the invention, the catalyst modifier is included(combined) with the polymerization catalyst system before adding thecombination directly to a reaction zone.

In an embodiment of the invention, the catalyst modifier is added to apolymer seed bed present in a reactor prior to starting thepolymerization reaction by introduction of a catalyst.

In an embodiment of the invention, the catalyst modifier is addeddirectly to a reaction zone, separately from a polymerization catalystsystem, and the catalyst modifier is added as a mixture with an inerthydrocarbon.

In an embodiment of the invention, the catalyst modifier is addeddirectly to a reaction zone, separately from a polymerization catalystsystem, and the catalyst modifier is added as a mixture with an inerthydrocarbon, and is added during a polymerization reaction.

The total amount of catalyst modifier that may be fed to a reactorand/or included in the polymerization catalyst system is notspecifically limited, but it should not exceed an amount which causesthe organotransition metal based polymerization catalyst system activityto drop to below that which would be commercially acceptable.

In this regard, the amount of catalyst modifier fed to a reactor willgenerally not exceed about 150 ppm, or about 100 ppm, or about 75 ppm,or about 50 ppm, or about 25 ppm (parts per million based on the weightof the (co)polymer being produced) while the amount of catalyst modifierincluded in the polymerization catalyst system will generally not exceedabout 10 weight percent (based on the total weight of the polymerizationcatalyst system, including the catalyst modifier).

In embodiments of the invention, the catalyst modifier fed to a reactorwill be from about 150 to 0 ppm, and including narrower ranges withinthis range, such as but not limited to, from about 150 to about 1 ppm,or from about 150 to about 5 ppm, or from about 100 to 0 ppm, or fromabout 100 to about 1 ppm, or from about 100 to about 5 ppm, or fromabout 75 to 0 ppm, or from about 75 to about 1 ppm, or from about 75 toabout 5 ppm, or from about 50 to 0 ppm, or from about 50 to about 1 ppm,or from about 50 to about 5 ppm, or from about 25 to 0 ppm, or fromabout 25 to about 1 ppm, or from about 25 to about 5 ppm (parts permillion by weight of the polymer being produced).

In embodiments of the invention, the amount of catalyst modifierincluded in the polymerization catalyst system will be from 0 to about10 weight percent, and including narrower ranges within this range, suchas but not limited to, from 0 to about 6.0 weight percent, or from about0.25 to about 6.0 weight percent, or from 0 to about 5.0 weight percent,or from about 0.25 to about 5.0 weight percent, or from 0 to about 4.5weight percent, or from about 0.5 to about 4.5 weight percent, or fromabout 1.0 to about 4.5 weight percent, or from about 0.75 to about 4.0weight percent, or from 0 to about 4.0 weight percent, or from about 0.5to about 4.0 weight percent, or from about 1.0 to about 4.0 weightpercent, or from 0 to about 3.75 weight percent, or from about 0.25 toabout 3.75 weight percent, or from about 0.5 to about 3.5 weightpercent, or from about 1.25 to about 3.75 weight percent, or from about1.0 to about 3.5 weight percent, or from about 1.5 to about 3.5 weightpercent, or from about 0.75 to about 3.75 weight percent, or from about1.0 to about 3.75 weight percent (wt % is the weight percent of thecatalyst modifier based on the total weight of the polymerizationcatalyst system; e.g. the combined weight of an organotransition metalcatalyst, an inert support, a catalyst activator and a catalystmodifier).

Other catalyst modifiers may be used and include compounds such ascarboxylate metal salts (see U.S. Pat. Nos. 7,354,880; 6,300,436;6,306,984; 6,391,819; 6,472,342 and 6,608,153 for examples),polysulfones, polymeric polyamines and sulfonic acids (see U.S. Pat.Nos. 6,562,924; 6,022,935 and 5,283,278 for examples).Polyoxyethylenealkylamines, which are described in for example inEuropean Pat. Appl. No. 107,127, may also be used. Further catalystmodifiers include aluminum stearate and aluminum oleate. Catalystmodifiers are supplied commercially under the trademarks OCTASTAT™ andSTADIS™. The catalyst modifier STADIS is described in U.S. Pat. Nos.7,476,715; 6,562,924 and 5,026,795 and is available from Octel Starreon.STADIS generally comprises a polysulfone copolymer, a polymeric amineand an oil soluble sulfonic acid.

Commercially available catalyst modifiers sometimes contain unacceptableamounts of water for use with polymerization catalysts. Accordingly, thecatalyst modifier may be treated with a substance which removes water(e.g. by reaction therewith to form inert products, or adsorption orabsorption methods), such as a metal alkyl scavenger or molecularsieves. See for example, U.S. Pat. Appl. Pub. No. 2011/0184124 for useof a scavenger compound to remove water from a metal carboxylateantistatic agent. Alternatively, a catalyst modifier may be dried underreduced pressure and elevated temperatures to reduce the amount of waterpresent (see the Examples section below). For example, a catalystmodifier may be treated with elevated temperatures (e.g. at least about10° C. above room temperature or ambient temperature) under reducedpressure (e.g. below atmospheric pressure) to distill off water, as canbe achieved by using a dynamic vacuum pump.

Scavenger

Optionally, scavengers are added to the polymerization process. Anysuitable scavenger or scavengers can be used. Scavengers are well knownin the art.

In an embodiment of the invention, scavengers are organoaluminumcompounds having the formula: Al³(X³)_(n)(X⁴)_(3-n), where (X³) is ahydrocarbyl having from 1 to about 20 carbon atoms; (X⁴) is selectedfrom alkoxide or aryloxide, any one of which having from 1 to about 20carbon atoms; halide; or hydride; and n is a number from 1 to 3,inclusive; or alkylaluminoxanes having the formula: R³₂Al¹O(R³Al¹O)_(m)Al¹R³ ₂

wherein each R³ is independently selected from the group consisting ofC₁₋₂₀ hydrocarbyl radicals and m is from about 3 to about 50. Somenon-limiting examples of scavengers include triisobutylaluminum,triethylaluminum, trimethylaluminum or other trialkylaluminum compounds.

The scavenger may be used in any suitable amount but by way ofnon-limiting examples only, can be present in an amount to provide amolar ratio of Al:M (where M is the metal of the organometalliccompound) of from about 20 to about 2000, or from about 50 to about1000, or from about 100 to about 500. Generally the scavenger is addedto the reactor prior to the catalyst and in the absence of additionalpoisons and over time declines to about 0, or is added continuously.

Optionally, the scavengers may be independently supported. For example,an inorganic oxide that has been treated with an organoaluminum compoundor alkylaluminoxane may be added to the polymerization reactor. Themethod of addition of the organoaluminum or alkylaluminoxane compoundsto the support is not specifically defined and is carried out byprocedures well known in the art.

The Ethylene Copolymer Composition

The term “ethylene copolymer” is used herein interchangeably with theterm “copolymer”, or “polyethylene copolymer” and all connote a polymerconsisting of polymerized ethylene units and at least one type ofpolymerized alpha olefin.

In some embodiments of the present invention, the ethylene copolymercompositions are not polymer blends, but optionally they may be used asa component in a polymer blend. The term polymer “blend” is herein meantto connote a dry blend of two dissimilar or different polymers,in-reactor blends arising from the use of multi or mixed catalystsystems in a single reactor zone, and blends that result from the use ofone catalyst in at least two reactors operating under differentpolymerization conditions, or blends involving the use of at least twodistinct catalysts in one or more reactors under the same or differentconditions (e.g. a blend resulting from in series reactors each runningunder different conditions or with different catalysts).

In one embodiment, the ethylene copolymer compositions are copolymers ofethylene and an alpha olefin selected from 1-butene, 1-hexene and1-octene.

In embodiments of the invention, the ethylene copolymer composition willcomprise at least about 75 weight % of ethylene units, or at least about80 wt % of ethylene units, or at least about 85 wt % of ethylene unitswith the balance being an alpha-olefin unit, based on the weight of theethylene copolymer composition.

In embodiments of the invention, the ethylene copolymer will have a meltindex (I₂) of from about 0.01 to about 3.0 g/10 min, or from about 0.1to about 2.5 g/10 min, or from about 0.1 to about 2.0 g/10 min, or fromabout 0.25 to about 2.0 g/10 min, or from about 0.01 to about 1.0 g/10min, or from about 0.1 to about 1.0 g/10 min, or less than about 1.0g/10 min, or from about 0.1 to less than about 1.0 g/10 min, or fromabout 0.25 to about 1.0 g/10 min, or from about 0.25 to about 0.9 g/10min, or from about 0.25 to about 0.80 g/10 min, or from about 0.2 toabout 0.9 g/10 min, or from about 0.20 to about 0.85 g/10 min, or fromabout 0.25 to about 0.85 g/10 min. In embodiments of the invention, theethylene copolymer will have a melt index (I₂) of from greater thanabout 1.0 to about 2.0 g/10 min, or from greater than about 1.0 to about1.75 g/10 min, or from greater than about 1.0 to about 1.5 g/10 min.

In embodiments of the invention, the ethylene copolymer will have adensity of from about 0.916 g/cc to about 0.936 g/cc including narrowerranges within this range, such as for example, from about 0.916 g/cc toabout 0.935 g/cc, or from about 0.916 g/cc to about 0.932 g/cc, or fromabout 0.916 g/cc to about 0.930 g/cc, or from about 0.917 g/cc to about0.932 g/cc, or from about 0.916 g/cc to about 0.930 g/cc, or from about0.917 g/cc to about 0.930 g/cc, or from about 0.916 g/cc to about 0.925g/cc, or from about 0.917 g/cc to about 0.927 g/cc, or from about 0.917g/cc to about 0.926 g/cc, or from about 0.917 g/cc to about 0.925 g/cc,or from about 0.917 g/cc to about 0.923 g/cc, or from about 0.918 g/ccto about 0.932 g/cc, or from about 0.918 g/cc to about 0.930 g/cc, orfrom about 0.918 to about 0.930 g/cc, or from about 0.918 to about 0.928g/cc, or from about 0.920 to about 0.935 (note: “g” stands for gram;“cc” stands for cubic centimeter, cm³)

In an embodiment of the invention, the ethylene copolymer will have adensity of from about 0.916 g/cc to about 0.936 g/cc. In an embodimentof the invention, the ethylene copolymer will have a density of greaterthan about 0.916 g/cc to less than about 0.930 g/cc. In an embodiment ofthe invention, the ethylene copolymer will have a density of from about0.917 g/cc to about 0.927 g/cc. In an embodiment of the invention, theethylene copolymer composition will have a density of from about 0.918g/cc to about 0.927 g/cc.

The ethylene copolymers may have a unimodal, broad unimodal, bimodal, ormultimodal profile in a gel permeation chromatography (GPC) curvegenerated according to the method of ASTM D6474-99. The term “unimodal”is herein defined to mean there will be only one significant peak ormaximum evident in the GPC-curve. A unimodal profile includes a broadunimodal profile. By the term “bimodal” it is meant that in addition toa first peak, there will be a secondary peak or shoulder whichrepresents a higher or lower molecular weight component (i.e. themolecular weight distribution, can be said to have two maxima in amolecular weight distribution curve). Alternatively, the term “bimodal”connotes the presence of two maxima in a molecular weight distributioncurve generated according to the method of ASTM D6474-99. The term“multi-modal” denotes the presence of two or more maxima in a molecularweight distribution curve generated according to the method of ASTMD6474-99.

In an embodiment of the invention, the ethylene copolymer will have aunimodal profile in a gel permeation chromatography (GPC) curvegenerated according to the method of ASTM D6474-99

In embodiments of the invention, the ethylene copolymer will exhibit aweight average molecular weight (M_(W)) as determined by gel permeationchromatography (GPC) of from about 30,000 to about 250,000, includingnarrower ranges within this range, such as for example, from about50,000 to about 200,000, or from about 50,000 to about 175,000, or fromabout 75,000 to about 150,000, or from about 80,000 to about 130,000.

In embodiments of the invention, the ethylene copolymer will exhibit anumber average molecular weight (M_(n)) as determined by gel permeationchromatography (GPC) of from about 5,000 to about 100,000 includingnarrower ranges within this range, such as for example from about 7,500to about 100,000, or from about 7,500 to about 75,000, or from about7,500 to about 50,000, or from about 10,000 to about 100,000, or fromabout 10,000 to about 75,000, or from about 10,000 to about 50,000.

In embodiments of the invention, the ethylene copolymer will exhibit aZ-average molecular weight (M_(Z)) as determined by gel permeationchromatography (GPC) of from about 50,000 to about 1,000,000 includingnarrower ranges within this range, such as for example from about 75,000to about 750,000, or from about 100,000 to about 500,000, or from about100,000 to about 400,000, or from about 125,000 to about 375,000, orfrom about 150,000 to about 350,000, or from about 175,000 to about375,000, or from about 175,000 to about 400,000, or from about 200,000to about 400,000 or from about 225,000 to about 375,000.

In embodiments of the invention, the ethylene copolymer will have amolecular weight distribution (M_(w)/M_(n)) as determined by gelpermeation chromatography (GPC) of from about 3.5 to about 7.0,including narrower ranges within this range, such as for example, fromabout 3.5 to about 6.5, or from about 3.6 to about 6.5, or from about3.6 to about 6.0, or from about 3.5 to about 5.5, or from about 3.6 toabout 5.5, or from about 3.5 to about 5.0, or from about 4.5 to about6.0, or from about 4.0 to about 6.0, or from about 4.0 to about 5.5.

In embodiments of the invention, the ethylene copolymer will have a Zaverage molecular weight distribution (M_(z)/M_(w)) as determined by gelpermeation chromatography (GPC) of from about 2.0 to about 5.5,including narrower ranges within this range, such as for example, fromabout 2.0 to about 5.0, or from about 2.0 to about 4.5, or from about2.0 to about 4.0, or from about 2.0 to about 2.5, or from about 2.0 toabout 3.0, or from about 2.0 to about 3.5.

In an embodiment of the invention, the ethylene copolymer will have aflat comonomer incorporation profile as measured using Gel-PermeationChromatography with Fourier Transform Infra-Red detection (GPC-FTIR). Inan embodiment of the invention, the ethylene copolymer will have anegative (i.e. “normal”) comonomer incorporation profile as measuredusing GPC-FTIR. In an embodiment of the invention, the ethylenecopolymer will have an inverse (i.e. “reverse”) or partially inversecomonomer incorporation profile as measured using GPC-FTIR. If thecomonomer incorporation decreases with molecular weight, as measuredusing GPC-FTIR, the distribution is described as “normal” or “negative”.If the comonomer incorporation is approximately constant with molecularweight, as measured using GPC-FTIR, the comonomer distribution isdescribed as “flat” or “uniform”. The terms “reverse comonomerdistribution” and “partially reverse comonomer distribution” mean thatin the GPC-FTIR data obtained for the copolymer, there is one or morehigher molecular weight components having a higher comonomerincorporation than in one or more lower molecular weight segments. Theterm “reverse(d) comonomer distribution” is used herein to mean, thatacross the molecular weight range of the ethylene copolymer, comonomercontents for the various polymer fractions are not substantially uniformand the higher molecular weight fractions thereof have proportionallyhigher comonomer contents (i.e. if the comonomer incorporation riseswith molecular weight, the distribution is described as “reverse” or“reversed”). Where the comonomer incorporation rises with increasingmolecular weight and then declines, the comonomer distribution is stillconsidered “reverse”, but may also be described as “partially reverse”.

In an embodiment of the invention the ethylene copolymer has a reversedcomonomer incorporation profile as measured using GPC-FTIR.

In an embodiment of the invention, the ethylene copolymer will have acomonomer incorporation profile as determined by GPC-FTIR whichsatisfies the following condition: SCB/1000C at MW of 200,000−SCB/1000Cat MW of 50,000 is a greater than 0; where “−” is a minus sign,SCB/1000C is the comonomer content determined as the number of shortchain branches per thousand carbons and MW is the correspondingmolecular weight (i.e. the absolute molecular weight) on a GPC orGPC-FTIR chromatograph.

In an embodiment of the invention, the ethylene copolymer will have acomonomer incorporation profile as determined by GPC-FTIR whichsatisfies the following condition: SCB/1000C at MW of 200,000−SCB/1000Cat MW of 50,000 is greater than 1.0; where SCB/1000C is the comonomercontent determined as the number of short chain branches per thousandcarbons and MW is the corresponding molecular weight (i.e. the absolutemolecular weight) on a GPC or GPC-FTIR chromatograph.

In an embodiment of the invention, the ethylene copolymer will have acomonomer incorporation profile as determined by GPC-FTIR whichsatisfies the following condition: SCB/1000C at MW of 200,000−SCB/1000Cat MW of 50,000 is greater than 2.0; where SCB/1000C is the comonomercontent determined as the number of short chain branches per thousandcarbons and MW is the corresponding molecular weight (i.e. the absolutemolecular weight) on a GPC or GPC-FTIR chromatograph.

In an embodiment of the invention, the ethylene copolymer will have acomonomer incorporation profile as determined by GPC-FTIR whichsatisfies the following condition: SCB/1000C at MW of 200,000−SCB/1000Cat MW of 50,000>3.0; where SCB/1000C is the comonomer content determinedas the number of short chain branches per thousand carbons and MW is thecorresponding molecular weight (i.e. the absolute molecular weight) on aGPC or GPC-FTIR chromatograph.

In an embodiment of the invention, the ethylene copolymer will have acomonomer incorporation profile as determined by GPC-FTIR whichsatisfies the following condition: SCB/1000C at MW of 200,000−SCB/1000Cat MW of 50,000>4.0; where SCB/1000C is the comonomer content determinedas the number of short chain branches per thousand carbons and MW is thecorresponding molecular weight (i.e. the absolute molecular weight) on aGPC or GPC-FTIR chromatograph.

In an embodiment of the invention, the ethylene copolymer will have acomonomer incorporation profile as determined by GPC-FTIR whichsatisfies the following condition: SCB/1000C at MW of 200,000−SCB/1000Cat MW of 50,000>5.0; where SCB/1000C is the comonomer content determinedas the number of short chain branches per thousand carbons and MW is thecorresponding molecular weight (i.e. the absolute molecular weight) on aGPC or GPC-FTIR chromatograph.

In an embodiment of the invention, the ethylene copolymer will have acomonomer incorporation profile as determined by GPC-FTIR whichsatisfies the following condition: SCB/1000C at MW of 200,000−SCB/1000Cat MW of 50,000>6.0; where SCB/1000C is the comonomer content determinedas the number of short chain branches per thousand carbons and MW is thecorresponding molecular weight (i.e. the absolute molecular weight) on aGPC or GPC-FTIR chromatograph.

In an embodiment of the invention, the ethylene copolymer will have acomonomer incorporation profile as determined by GPC-FTIR whichsatisfies the following condition: SCB/1000C at MW of 200,000−SCB/1000Cat MW of 50,000 of from 2.0 to 8.0 including narrower ranges within thisrange; where SCB/1000C is the comonomer content determined as the numberof short, chain branches per thousand carbons and MW is thecorresponding molecular weight (i.e. the absolute molecular weight) on aGPC or GPC-FTIR chromatograph.

In an embodiment of the invention, the ethylene copolymer will have acomonomer incorporation profile as determined by GPC-FTIR whichsatisfies the following condition: SCB/1000C at MW of 200,000−SCB/1000Cat MW of 50,000 of from 3.0 to 7.0 including narrower ranges within thisrange; where SCB/1000C is the comonomer content determined as the numberof short chain branches per thousand carbons and MW is the correspondingmolecular weight (i.e. the absolute molecular weight) on a GPC orGPC-FTIR chromatograph.

In an embodiment of the invention, the ethylene copolymer will have amelt flow ratio (the MFR=I₂₁/I₂) of from about 28 to about 60 or fromabout 30 to about 60 or from about 32 to about 60. In furtherembodiments of the invention, the ethylene copolymer will have an I₂₁/I₂of from about 30 to about 55, or from about 30 to about 50, or fromabout 30 to about 45, or from about 32 to about 50 or from about 35 toabout 55, or from about 36 to about 50, or from about 36 to about 48, orfrom about 36 to about 46, or from about 35 to about 50, or from greaterthan about 35 to less than about 50, or from greater than about 35 toabout 50.

In an embodiment of the invention, the ethylene copolymer has a meltflow ratio (I₂₁/I₂) of from greater than about 30 to about 50. In anembodiment of the invention, the ethylene copolymer has a melt flowratio (I₂₁/I₂) of from about 32 to about 50. In an embodiment of theinvention, the ethylene copolymer has a melt flow ratio (I₂₁/I₂) of fromabout 35 to about 50. In an embodiment of the invention, the ethylenecopolymer has a melt flow ratio (I₂₁/I₂) of from about 30 to about 55.In an embodiment of the invention, the ethylene copolymer has a meltflow ratio (I₂₁/I₂) of from about 32 to about 55. In an embodiment ofthe invention, the ethylene copolymer has a melt flow ratio (I₂₁/I₂) offrom about 35 to about 55.

In embodiments of the invention, the ethylene copolymer will have acomposition distribution breadth index CDBI₅₀, as determined bytemperature elution fractionation (TREF) of from about 40% to about 75%by weight, or from about 45% to about 75% by weight, or from about 50%to about 75% by weight, or from about 55% to about 75% by weight, orfrom about 60% to about 75% by weight. In embodiments of the invention,the ethylene copolymer will have a CDBI₅₀ of from about 50% to about70%, or about 55% to about 70%, or from about 50% to about 69%, or fromabout 55% to about 69%, or from about 55% to about 65%, or from about60% to about 75%, or from about 60% to about 70%, or from about 60% toabout 69%, or from about 55% to about 67%, or from about 60% to about66% (by weight).

In an embodiment of the invention, the ethylene copolymer has a CDBI₅₀of from about 50 wt % to about 77 wt %. In an embodiment of theinvention, the ethylene copolymer has a CDBI₅₀ of from about 55 wt % toabout 75 wt %. In an embodiment of the invention, the ethylene copolymerhas a CDBI₅₀ of from about 60 wt % to about 73 wt %.

The composition distribution of an ethylene copolymer may also becharacterized by the T(75)−T(25) value, where the T(25) is thetemperature at which about 25 wt % of the eluted copolymer is obtained,and T(75) is the temperature at which about 75 wt % of the elutedcopolymer is obtained in a TREF experiment.

In an embodiment of the present invention, the ethylene copolymer willhave a T(75)−T(25) of from about 5 to about 25° C. as determined byTREF. In an embodiment of the present invention, the ethylene copolymerwill have a T(75)−T(25) of from about 7 to about 25° C. as determined byTREF. In an embodiment of the present invention, the ethylene copolymerwill have a T(75)−T(25) of from about 10 to about 25° C. as determinedby TREF. In an embodiment of the present invention, the ethylenecopolymer will have a T(75)−T(25) of from about 7 to about 22.5° C. asdetermined by TREF. In an embodiment of the present invention, theethylene copolymer will have a T(75)−T(25) of from about 7.0 to about20° C. as determined by TREF. In an embodiment of the present invention,the ethylene copolymer will have a T(75)−T(25) of from about 5 to about17.5° C. as determined by TREF. In an embodiment of the presentinvention, the ethylene copolymer will have a T(75)−T(25) of from about7 to about 17.5° C. as determined by TREF.

In embodiments of the invention, the ethylene copolymer will have a CYa-parameter (also called the Carreau-Yasuda shear exponent) of fromabout 0.01 to about 0.4, or from about 0.05 to about 0.4, or from about0.05 to about 0.3, or from about 0.01 to about 0.3, or from about 0.01to about 0.25, or from about 0.05 to about 0.30, or from about 0.05 toabout 0.25.

In embodiments of the invention, the ethylene copolymer will have anormalized shear thinning index, SHI @0.1 rad/s (i.e. the η*_(0.1)/η₀)of from about 0.001 to about 0.90, or from about 0.001 to about 0.8, orfrom about 0.001 to about 0.5, or less than about 0.9, or less thanabout 0.8, or less than about 0.5.

In an embodiment of the invention, the ethylene copolymer will have aTREF profile, as measured by temperature rising elution fractionation,which is multimodal, comprising at least two elution intensity maxima orpeaks.

In an embodiment of the invention, the ethylene copolymer will have anamount of copolymer eluting at a temperature at or below about 40° C.,of less than about 5 wt % as determined by temperature rising elutionfractionation (TREF).

In an embodiment of the invention, the ethylene copolymer will have anamount of copolymer eluting at a temperature of from about 90° C. toabout 105° C., of from about 5 to about 30 wt % as determined bytemperature rising elution fractionation (TREF). In an embodiment of theinvention, from about 5 to about 25 wt % of the ethylene copolymer willbe represented within a temperature range of from about 90° C. to about105° C. in a TREF profile. In an embodiment of the invention, from about7.5 to about 25 wt % of the ethylene copolymer will be representedwithin a temperature range of from about 90° C. to about 105° C. in aTREF profile. In an embodiment of the invention, from about 10 to about25 wt % of the ethylene copolymer will be represented within atemperature range of from about 90° C. to about 105° C. in a TREFprofile. In another embodiment of the invention, from about 5 to about22.5 wt % of the ethylene copolymer will be represented at a temperaturerange of from about 90° C. to about 105° C. in a TREF profile. Inanother embodiment of the invention, from about 5 to about 20.0 wt % ofthe ethylene copolymer will be represented at a temperature range offrom about 90° C. to about 105° C. in a TREF profile.

In embodiments of the invention, less than about 1 wt %, or less thanabout 0.5 wt %, or less than about 0.05 wt %, or about 0 wt % of theethylene copolymer will elute at a temperature of above about 100° C. ina TREF analysis.

In an embodiment of the invention, the ethylene copolymer will have aTREF profile, as measured by temperature rising elution fractionation,comprising: i) a multimodal TREF profile comprising at least two elutionintensity maxima (or peaks); ii) less than about 5 wt % of the copolymerrepresented at a temperature at or below about 40° C.; and iii) fromabout 5 to about 25 wt % of the copolymer represented at a temperatureof from about 90° C. to about 105° C.

In an embodiment of the invention, the ethylene copolymer has amultimodal TREF profile comprising at least two elution intensity maxima(or peaks).

In an embodiment of the invention, the ethylene copolymer has amultimodal TREF profile defined by at least two intensity maxima (orpeaks) occurring at elution temperatures T(low), and T(high), whereT(low) is from about 60° C. to about 87° C., and T(high) is from about88° C. to about 100° C.

In an embodiment of the invention, the ethylene copolymer has amultimodal TREF profile defined by at least two intensity maxima (orpeaks) occurring at elution temperatures T(low), and T(high), whereT(low) is from about 62° C. to about 87° C., and T(high) is from about89° C. to about 100° C.

In an embodiment of the invention, the ethylene copolymer has amultimodal TREF profile defined by at least two intensity maxima (orpeaks) occurring at elution temperatures T(low), and T(high), whereT(low) is from about 65° C. to about 85° C., and T(high) is from about90° C. to about 100° C.

In an embodiment of the invention, the ethylene copolymer has amultimodal TREF profile defined by at least two intensity maxima (orpeaks) occurring at elution temperatures T(low), and T(high), whereT(low) is from about 65° C. to about 85° C., and T(high) is from about90° C. to about 98° C.

In an embodiment of the invention, the ethylene copolymer has amultimodal TREF profile defined by at least two intensity maxima (orpeaks) occurring at elution temperatures T(low), and T(high), whereT(low) is from about 70° C. to about 85° C., and T(high) is from about90° C. to about 98° C.

In an embodiment of the invention, the ethylene copolymer has amultimodal TREF profile defined by at least two intensity maxima (orpeaks) occurring at elution temperatures T(low), and T(high), whereT(low) is from about 70° C. to about 80° C., and T(high) is from about90° C. to about 98° C.

In an embodiment of the invention, the ethylene copolymer has amultimodal TREF profile defined by at least two intensity maxima (orpeaks) occurring at elution temperatures T(low), and T(high), whereT(low) is from about 70° C. to about 80° C., and T(high) is from about90° C. to about 95° C.

In an embodiment of the invention, the ethylene copolymer has amultimodal TREF profile defined by at least two elution intensity maxima(or peaks) occurring at elution temperatures T(low), and T(high), where(high)-T(low) is from about 7.5° C. to about 35° C., or from about 10.0°C. to about 30° C., or from about 12.5° C. to about 30° C., or fromabout 7.0° C. to about 27° C., or from about 7° C. to about 25° C., orfrom about 10° C. to about 27° C., or from about 10° C. to about 25° C.,or from about 10° C. to about 22.5° C., or from about 12.5° C. to about22.5° C.

In an embodiment of the invention, the ethylene copolymer has amultimodal TREF profile defined by at least two intensity maxima (orpeaks) occurring at elution temperatures T(low), and T(high), whereT(low) is from about 65° C. to about 85° C., and T(high) is from about90° C. to about 98° C., where (high)-T(low) is from about 7.5° C. toabout 35° C., or from about 10.0° C. to about 30° C., or from about12.5° C. to about 30° C., or from about 7.0° C. to about 27° C., or fromabout 7° C. to about 25° C., or from about 10° C. to about 27° C., orfrom about 10° C. to about 25° C., or from about 10° C. to about 22.5°C., or from about 12.5° C. to about 22.5° C.

In an embodiment of the invention, the ethylene copolymer has amultimodal TREF profile comprising at least three elution intensitymaxima (or peaks).

In an embodiment of the invention, the ethylene copolymer has a trimodalTREF profile comprising three elution intensity maxima (or peaks).

In an embodiment of the invention, the ethylene copolymer has amultimodal TREF profile defined by three elution intensity maxima (orpeaks) occurring at elution temperatures T(low), T(medium or “med” forshort) and T(high), where the intensity of the peaks at T(low) andT(high) is greater than the intensity of the peak at T(med).

In an embodiment of the invention, the ethylene copolymer has amultimodal TREF profile defined by three elution intensity maxima (orpeaks) occurring at elution temperatures T(low), T(medium or “med” forshort) and T(high), where T(low) is from about 60° C. to about 87° C.,T(high) is from about 88° C. to about 100° C., and T(med) is higher thanT(low), but lower than T(high).

In an embodiment of the invention, the ethylene copolymer has amultimodal TREF profile defined by three elution intensity maxima (orpeaks) occurring at elution temperatures T(low), T(medium or “med” forshort) and T(high), where T(low) is from about 62° C. to about 87° C.,T(high) is from about 89° C. to about 100° C., and T(med) is higher thanT(low), but lower than T(high).

In an embodiment of the invention, the ethylene copolymer has amultimodal TREF profile defined by three elution intensity maxima (orpeaks) occurring at elution temperatures T(low), T(medium or “med” forshort) and T(high), where T(low) is from about 65° C. to about 85° C.,T(high) is from about 90° C. to about 100° C., and T(med) is higher thanT(low), but lower than T(high).

In an embodiment of the invention, the ethylene copolymer has amultimodal TREF profile defined by three elution intensity maxima (orpeaks) occurring at elution temperatures T(low), T(medium or “med” forshort) and T(high), where T(low) is from about 65° C. to about 85° C.,T(high) is from about 90° C. to about 98° C., and T(med) is higher thanT(low), but lower than T(high).

In an embodiment of the invention, the ethylene copolymer has amultimodal TREF profile defined by three elution intensity maxima (orpeaks) occurring at elution temperatures T(low), T(medium or “med” forshort) and T(high), where T(low) is from about 65° C. to about 80° C.,T(high) is from about 90° C. to about 98° C., and T(med) is higher thanT(low), but lower than T(high).

In an embodiment of the invention, the ethylene copolymer has amultimodal TREF profile defined by three elution intensity maxima (orpeaks) occurring at elution temperatures T(low), T(medium or “med” forshort) and T(high), where T(low) is from about 65° C. to about 87° C.,T(high) is from about 88° C. to about 100° C., and T(med) is higher thanT(low), but lower than T(high), where (high)-T(low) is from about 7.5°C. to about 35° C., or from about 10.0° C. to about 30° C., or fromabout 12.5° C. to about 30° C., or from about 7.0° C. to about 27° C.,or from about 7° C. to about 25° C., or from about 10° C. to about 27°C., or from about 10° C. to about 25° C.

In an embodiment of the invention, the ethylene copolymer has amultimodal TREF profile defined by three elution intensity maxima (orpeaks) occurring at elution temperatures T(low), T(medium or “med” forshort) and T(high), where T(low) is from about 62° C. to about 82° C.,T(med) is from about 76° C. to about 89° C. but is higher than T(low),and T(high) is from about 90° C. to about 100° C. In an embodiment ofthe invention, the ethylene copolymer has a multimodal TREF profiledefined by three elution intensity maxima (or peaks) occurring atelution temperatures T(low), T(medium or “med” for short) and T(high),where T(low) is from about 65° C. to about 80° C., T(med) is from about75° C. to about 90° C. but is higher than T(low), and T(high) is fromabout 90° C. to about 100° C. but is higher than T(med). In anembodiment of the invention, the ethylene copolymer has a multimodalTREF profile defined by three elution intensity maxima (or peaks)occurring at elution temperatures T(low), T(medium or “med” for short)and T(high), where T(low) is from about 67° C. to about 78° C., T(med)is from about 79° C. to about 89° C., and T(high) is from about 90° C.to about 100° C. In an embodiment of the invention, the ethylenecopolymer has a multimodal TREF profile defined by three elutionintensity maxima (or peaks) occurring at elution temperatures T(low),T(medium or “med” for short) and T(high), where T(low) is from about 67°C. to about 78° C., T(med) is from about 80° C. to about 87° C., andT(high) is from about 88° C. to about 98° C.

In embodiments of the invention, the ethylene copolymer has a multimodalTREF profile defined by three elution intensity maxima (or peaks)occurring at elution temperatures T(low), T(medium or “med” for short)and T(high), where T(med)-T(low) is from about 3° C. to about 25° C., orfrom about 5° C. to about 20° C.; or from about 5° C. to about 15° C.,or from about 7° C. to about 15° C.

In embodiments of the invention, the ethylene copolymer has a multimodalTREF profile defined by three elution intensity maxima (or peaks)occurring at elution temperatures T(low), T(medium or “med” for short)and T(high), where T(high)-T(med) is from about 3° C. to about 20° C.,or from about 3° C. to about 17° C., or from about 3° C. to about 15°C., or from about 5° C. to about 20° C., or from about 5° C. to about17° C., or from about 5° C. to about 15° C., or from about 7° C. toabout 17° C., or from about 7° C. to about 15° C. or from about 10° C.to about 17° C., or from about 10° C. to about 15° C.

In embodiments of the invention, the ethylene copolymer has a multimodalTREF profile defined by three elution intensity maxima (or peaks)occurring at elution temperatures T(low), T(medium or “med” for short)and T(high), where T(high)-T(low) is from about 15° C. to about 35° C.,or from about 15° C. to about 30° C., or from about 17° C. to about 30°C., or from about 15° C. to about 27° C., or from about 17° C. to about27° C., or from about 20° C. to about 30° C. or from about 20° C. toabout 27° C., or from about 15° C. to about 25° C. or from about 15° C.to about 22.5° C.

In an embodiment of the invention, the ethylene copolymer has amultimodal TREF profile comprises three elution intensity maxima (orpeaks) occurring at elution temperatures T(low), T(medium or “med” forshort) and T(high), where the intensity of the peaks at T(low) andT(high) are greater than the intensity of the peak at T(med); and whereT(med)-T(low) is from about 3° C. to about 25° C.; where T(high)-T(med)is from about 5° C. to about 15° C.; and where T(high)-T(low) is fromabout 15° C. to about 35° C.

In an embodiment of the invention, the ethylene copolymer has amultimodal TREF profile comprises three elution intensity maxima (orpeaks) occurring at elution temperatures T(low), T(medium or “med” forshort) and T(high), where the intensity of the peaks at T(low) andT(high) are greater than the intensity of the peak at T(med); and whereT(med)-T(low) is from about 3° C. to about 15° C.; where T(high)-T(med)is from about 5° C. to about 15° C.; and where T(high)-T(low) is fromabout 15° C. to about 30° C.

In an embodiment of the invention, the ethylene copolymer has twomelting peaks as measured by differential scanning calorimetry (DSC).

In embodiments of the invention, the ethylene copolymer will have ahexane extractables level of ≦about 3.0 wt %, or ≦about 2.0 wt %, or≦about 1.5 wt % or ≦about 1.0 wt %. In an embodiment of the invention,the copolymer has a hexane extractables level of from about 0.2 to about3.0 wt %, or from about 0.2 to about 2.5 wt %, or from about 0.2 toabout 2.0 wt %, or from about 0.2 to about 1.0 wt %.

In an embodiment of the invention, the ethylene copolymer satisfies therelationship: (M_(w)/M_(n))≧72 [(I₂₁/I₂)⁻¹+10⁻⁶ (M_(n))].

In an embodiment of the invention, the ethylene copolymer satisfies therelationship δ^(XO)≦83.0−1.25 (CDBI₅₀)/(M_(w)/M_(n)), where δ^(XO) isthe crossover phase angle from a Van Gurp-Palmen (VGP) plot asdetermined by dynamic mechanical analysis (DMA) and CDBI₅₀ is thecomonomer distribution breadth index as determined by TREF analysis.

In embodiments of the invention, the ethylene copolymer has a δ^(XO) ofless than about 70° or from about 55° to about 70°, where δ^(XO) is thecrossover phase angle from a van Gurp-Palmen (VGP) plot as determined bydynamic mechanical analysis (DMA) and CDBI₅₀ is the comonomerdistribution breadth index as determined by TREF analysis. In anembodiment of the invention, the ethylene copolymer satisfies therelationship: δ^(XO)≦80.7−(CDBI₅₀)/(M_(w)/M_(n)) at a δ^(XO) of fromabout 55° to about 70°, where δ^(XO) is the crossover phase angle from avan Gurp-Palmen (VGP) plot as determined by dynamic mechanical analysis(DMA) and CDBI₅₀ is the comonomer distribution breadth index asdetermined by TREF analysis.

In an embodiment of the invention, the ethylene copolymer satisfies thefollowing relationship: (M_(w)/M_(n))≧72 [(I₂₁/I₂)⁻¹+10⁻⁶ (M_(n))] andhas a δ^(XO) or from about 55° to about 70°, where δ^(XO) is thecrossover phase angle from a van Gurp-Palmen (VGP) plot as determined bydynamic mechanical analysis (DMA) and CDBI₅₀ is the comonomerdistribution breadth index as determined by TREF analysis.

In an embodiment of the invention, the ethylene copolymer satisfies thefollowing relationships: (M_(w)/M_(n))≧72 [(I₂₁/I₂)⁻¹+10⁻⁶ (M_(n))] andδ^(XO)≦83.0−1.25 (CDBI₅₀)/(M_(w)/M_(n)), where δ^(XO) is the crossoverphase angle from a van Gurp-Palmen (VGP) plot as determined by dynamicmechanical analysis (DMA) and CDBI₅₀ is the comonomer distributionbreadth index as determined by TREF analysis.

In an embodiment of the invention, the ethylene copolymer satisfies thefollowing relationships: (M_(w)/M_(n))≧72 [(I₂₁/I₂)⁻¹+10⁻⁶ (M_(n))]; andδ^(XO)≦80.7−(CDBI₅₀)/(M_(w)/M_(n)) at a δ^(XO) of from about 55° toabout 70°; where δ^(XO) is the crossover phase angle from a vanGurp-Palmen (VGP) plot as determined by dynamic mechanical analysis(DMA) and CDBI₅₀ is the comonomer distribution breadth index asdetermined by TREF analysis.

In an embodiment of the invention, the ethylene copolymer satisfies thefollowing relationships: (M_(w)/M_(n))≧72 [(I₂₁/I₂)⁻¹+10⁻⁶ (M_(n))];δ^(XO)≦80.7−(CDBI₅₀)/(M_(w)/M_(n)) at a δ^(XO) of from about 55° toabout 70°; and δ^(XO)≦83.0−1.25 (CDBI₅₀)/(M_(w)/M_(n)), where δ^(XO) isthe crossover phase angle from a van Gurp-Palmen (VGP) plot asdetermined by dynamic mechanical analysis (DMA) and CDBI₅₀ is thecomonomer distribution breadth index as determined by TREF analysis.

Film Production

The extrusion-blown film process is a well-known process for thepreparation of plastic film. The process employs an extruder whichheats, melts and conveys the molten plastic and forces it through anannular die. Typical extrusion temperatures are from about 330 to about500° F., especially about 350 to about 460° F.

The polyethylene copolymer film is drawn from the die and formed into atube shape and eventually passed through a pair of draw or nip rollers.Internal compressed air is then introduced from a mandrel causing thetube to increase in diameter forming a “bubble” of the desired size.Thus, the blown film is stretched in two directions, namely in the axialdirection (by the use of forced air which “blows out” the diameter ofthe bubble) and in the lengthwise direction of the bubble (by the actionof a winding element which pulls the bubble through the machinery).External air is also introduced around the bubble circumference to coolthe melt as it exits the die. Film width is varied by introducing moreor less internal air into the bubble thus increasing or decreasing thebubble size. Film thickness is controlled primarily by increasing ordecreasing the speed of the draw roll or nip roll to control thedraw-down rate.

The bubble is then collapsed immediately after passing through the drawor nip rolls. The cooled film can then be processed further by cuttingor sealing to produce a variety of consumer products. While not wishingto be bound by theory, it is generally believed by those skilled in theart of manufacturing blown films that the physical properties of thefinished films are influenced by both the molecular structure of theethylene copolymer and by the processing conditions. For example, theprocessing conditions are thought to influence the degree of molecularorientation (in both the machine direction and the axial or crossdirection).

A balance of “machine direction” (“MD”) and “transverse direction”(“TD”—which is perpendicular to MD) molecular orientation is generallyconsidered desirable for the films associated with some embodiments ofthe invention (for example, Dart Impact strength, Machine Direction andTransverse Direction tear properties may be affected).

Thus, it is recognized that these stretching forces on the “bubble” canaffect the physical properties of the finished film. In particular, itis known that the “blow up ratio” (i.e. the ratio of the diameter of theblown bubble to the diameter of the annular die) can have a significanteffect upon the dart impact strength and tear strength of the finishedfilm.

The above description relates to the preparation of monolayer films.Multilayer films may be prepared by 1) a “co-extrusion” process thatallows more than one stream of molten polymer to be introduced to anannular die resulting in a multi-layered film membrane or 2) alamination process in which film layers are laminated together.

In an embodiment of the invention, the films of this invention areprepared using the above described blown film process.

An alternative process is the so-called cast film process, wherein thepolyethylene is melted in an extruder, then forced through a linear slitdie, thereby “casting” a thin flat film. The extrusion temperature forcast film is typically somewhat hotter than that used in the blown filmprocess (with typically operating temperatures of from about 450 toabout 550° F.). In general, cast film is cooled (quenched) more rapidlythan blown film.

In an embodiment of the invention, the films of this invention areprepared using a cast film process.

Additives

The ethylene copolymer composition used to make films, may also containadditives, such as for example, primary antioxidants (such as hinderedphenols, including vitamin E); secondary antioxidants (especiallyphosphites and phosphonites); nucleating agents, plasticizers or polymerprocessing aids PPAs (e.g. fluoroelastomer and/or polyethylene glycolbound process aid), acid scavengers, stabilizers, anticorrosion agents,blowing agents, other ultraviolet light absorbers such as chain-breakingantioxidants, etc., quenchers, antistatic agents, slip agents,anti-blocking agent, pigments, dyes and fillers and cure agents such asperoxide.

These and other common additives in the polyolefin industry may bepresent in copolymer compositions from about 0.01 to about 50 wt % inone embodiment, and from about 0.1 to about 20 wt % in anotherembodiment, and from about 1 to about 5 wt % in yet another embodiment,wherein a desirable range may comprise any combination of any upper wt %limit with any lower wt % limit.

In an embodiment of the invention, antioxidants and stabilizers such asorganic phosphites and phenolic antioxidants may be present in thecopolymer compositions from about 0.001 to about 5 wt % in oneembodiment, and from about 0.01 to about 0.8 wt % in another embodiment,and from about 0.02 to about 0.5 wt % in yet another embodiment.Non-limiting examples of organic phosphites that are suitable aretris(2,4-di-tert-butylphenyl)phosphite (IRGAFOS 168) and tris(nonylphenyl) phosphite (WESTON 399). Non-limiting examples of phenolicantioxidants include octadecyl 3,5 di-t-butyl-4-hydroxyhydrocinnamate(IRGANOX 1076) and pentaerythrityltetrakis(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (IRGANOX 1010);and 1,3,5-Tri(3,5-di-tert-butyl-4-hydroxybenzyl-isocyanurate (IRGANOX3114).

Fillers may be present in the ethylene copolymer composition from about0.1 to about 50 wt % in one embodiment, and from about 0.1 to about 25wt % of the composition in another embodiment, and from about 0.2 toabout 10 wt % in yet another embodiment. Fillers include but are notlimited to titanium dioxide, silicon carbide, silica (and other oxidesof silica, precipitated or not), antimony oxide, lead carbonate, zincwhite, lithopone, zircon, corundum, spinel, apatite, Barytes powder,barium sulfate, magnesiter, carbon black, dolomite, calcium carbonate,talc and hydrotalcite compounds of the ions Mg, Ca, or Zn with Al, Cr orFe and CO₃ and/or HPO₄, hydrated or not; quartz powder, hydrochloricmagnesium carbonate, glass fibers, clays, alumina, and other metaloxides and carbonates, metal hydroxides, chrome, phosphorous andbrominated flame retardants, antimony trioxide, silica, silicone, andblends thereof. These fillers may include any other fillers and porousfillers and supports which are known in the art.

Fatty acid salts may also be present in the copolymer compositions. Suchsalts may be present from about 0.001 to about 2 wt % of the copolymercomposition in one embodiment, and from about 0.01 to about 1 wt % inanother embodiment. Examples of fatty acid metal salts include lauricacid, stearic acid, succinic acid, stearyl lactic acid, lactic acid,phthalic acid, benzoic acid, hydroxystearic acid, ricinoleic acid,naphthenic acid, oleic acid, palmitic acid, and erucic acid, suitablemetals including Li, Na, Mg, Ca, Sr, Ba, Zn, Cd, Al, Sn, Pb and soforth. Desirable fatty acid salts are selected from magnesium stearate,calcium stearate, sodium stearate, zinc stearate, calcium oleate, zincoleate, and magnesium oleate.

With respect to the physical process of producing the blend of theethylene copolymer and one or more additives, sufficient mixing shouldtake place to assure that a uniform blend will be produced prior toconversion into a finished product. The copolymer can be in any physicalform when used to blend with the one or more additives. In oneembodiment, reactor granules, defined as the granules of polymer thatare isolated from the polymerization reactor, are used to blend with theadditives. The reactor granules have an average diameter of from about10 μm to about 5 mm, and from about 50 μm to about 10 mm in anotherembodiment. Alternately, the ethylene copolymer is in the form ofpellets, such as, for example, having an average diameter of from about1 mm to about 6 mm that are formed from melt extrusion of the reactorgranules.

One method of blending the additives with the ethylene copolymer is tocontact the components in a tumbler or other physical blending means,the copolymer being in the form of reactor granules. This can then befollowed, if desired, by melt blending in an extruder. Another method ofblending the components is to melt blend the copolymer pellets with theadditives directly in an extruder, or any other melt blending means.

Film Properties.

Film (or film layer), is made from the ethylene copolymers defined asabove. Generally, an additive as described above is mixed with theethylene copolymer prior to film production. The ethylene copolymers andfilms have a balance of processing and mechanical properties.Accordingly, films may be made from an ethylene copolymer having a meltindex I₂ of below about 1.0 g/10 min, will have a dart impact strengthof about 400 g/mil, a about 1% MD secant modulus of greater than about140 MPa, and a about 1% TD secant modulus of greater than about 170 MPain combination with good film processing output rates. Alternatively,films can be made from an ethylene copolymer having a melt index I₂ ofbetween about 1 and about 2 g/10 min, will have a dart impact strengthof ≧about 200 g/mil, a about 1% MD secant modulus of greater than about190 MPa, and a about 1% TD secant modulus of greater than about 210 MPain combination with good film processing output rates.

In embodiments of the invention, the film will have a dart impact of≧about 400 g/mil, or ≧about 450 g/mil, or ≧about 500 g/mil, or ≧about550 g/mil, or ≧about 600 g/mil or ≧about 650 g/mil or ≧about 700 g/mil.In an embodiment of the invention, the film will have a dart impact offrom about 400 g/mil to about 950 g/mil. In an embodiment of theinvention, the film will have a dart impact of from about 400 g/mil toabout 850 g/mil. In another embodiment of the invention, the film willhave a dart impact of from about 400 g/mil to about 750 g/mil. Inanother embodiment of the invention, the film will have a dart impact offrom about 500 g/mil to about 950 g/mil. In another embodiment of theinvention, the film will have a dart impact of from about 500 g/mil toabout 850 g/mil. In a further embodiment of the invention, the film willhave dart impact of from about 500 g/mil to about 750 g/mil. In yetanother embodiment of the invention, the film will have dart impact offrom about 550 g/mil to about 950 g/mil. In yet another embodiment ofthe invention, the film will have dart impact of from about 550 g/mil toabout 850 g/mil. In yet another embodiment of the invention, the filmwill have dart impact of from about 550 g/mil to about 750 g/mil. Instill yet another embodiment of the invention, the film will have dartimpact of from about 600 g/mil to about 950 g/mil. In still yet anotherembodiment of the invention, the film will have dart impact of fromabout 600 g/mil to about 850 g/mil. In a further embodiment of theinvention, the film will have dart impact of from about 400 g/mil toabout 700 g/mil. In a further embodiment of the invention, the film willhave dart impact of from about 400 g/mil to about 650 g/mil.

In an embodiment of the invention, the film will have a dart impact of≧about 200 g/mil.

In embodiments of the invention, the film will have a ratio of MD tearto TD tear (MD tear/TD tear) of less than about 0.75, or ≦about 0.70, or≦about 0.60, or ≦about 0.50, or ≦about 0.45, or ≦about 0.40, or ≦about0.35, or ≦about 0.30. In another embodiment of the invention, the filmwill have a ratio of MD tear to TD tear of from about 0.010 to about0.75. In yet another embodiment of the invention, the film will have aratio of MD tear to TD tear of from about 0.05 to about 0.6. In stillanother embodiment of the invention, the film will have a ratio of MDtear to TD tear of from about 0.05 to about 0.55. In still yet furtherembodiments of the invention, the film will have a ratio of MD tear toTD tear of from about 0.1 to about 0.50 or from about 0.1 to about 0.35.

In embodiments of the invention, a ˜1 mil film will have a machinedirection (MD) secant modulus at about 1% strain of ≧about 140 MPa, or≧about 150 MPa, or ≧about 160 MPa, or ≧about 175 MPa, or ≧about 180 MPa≧about 190 MPa, or ≧about 200 MPa, or ≧about 210 MPa. In an embodimentof the invention, a ˜1 mil film will have a machine direction (MD)secant modulus at about 1% strain of from about 130 MPa to about 300MPa. In an embodiment of the invention, a ˜1 mil film will have amachine direction (MD) secant modulus at about 1% strain of from about140 MPa to about 300 MPa. In an embodiment of the invention, a ˜1 milfilm will have a machine direction (MD) secant modulus at about 1%strain of from about 140 MPa to about 275 MPa. In an embodiment of theinvention, a ˜1 mil film will have a machine direction (MD) secantmodulus at about 1% strain of from about 140 MPa to 250 MPa. In anembodiment of the invention, a ˜1 mil film will have a machine direction(MD) secant modulus at about 1% strain of from about 150 MPa to about260 MPa. In an embodiment of the invention, a ˜1 mil film will have amachine direction (MD) secant modulus at about 1% strain of from about160 MPa to about 260 MPa. In an embodiment of the invention, a ˜1 milfilm will have a machine direction (MD) secant modulus at about 1%strain of from about 160 MPa to about 250 MPa. In another embodiment ofthe invention, a ˜1 mil film will have a machine direction (MD) secantmodulus at about 1% strain of from about 170 MPa to about 250 MPa. Inyet another embodiment of the invention, a ˜1 mil film will have amachine direction (MD) secant modulus at about 1% strain of from about140 MPa to about 230 MPa. In yet another embodiment of the invention, a˜1 mil film will have a machine direction (MD) secant modulus at about1% strain of from about 180 MPa to about 280 MPa. In yet anotherembodiment of the invention, a ˜1 mil film will have a machine direction(MD) secant modulus at about 1% strain of from about 190 MPa to about280 MPa. In yet another embodiment of the invention, a ˜1 mil film willhave a machine direction (MD) secant modulus at about 1% strain of fromabout 180 MPa to about 260 MPa.

In an embodiment of the invention, a ˜1 mil film will have a transversedirection (TD) secant modulus at about 1% strain of ≧about 170 MPa, or≧about 180 MPa, or ≧about 190 MPa, or ≧about 200 MPa, or ≧about 210 MPa,or ≧about 220 MPa or ≧about 230 Mpa, or ≧about 240 Mpa, or ≧about 250Mpa. In an embodiment of the invention, a ˜1 mil film will have atransverse direction (TD) secant modulus at about 1% strain of fromabout 170 MPa to about 310 MPa. In an embodiment of the invention, a ˜1mil film will have a transverse direction (TD) secant modulus at about1% strain of from about 170 MPa to about 300 MPa. In an embodiment ofthe invention, a ˜1 mil film will have a transverse direction (TD)secant modulus at about 1% strain of from about 170 MPa to about 290MPa. In an embodiment of the invention, a ˜1 mil film will have atransverse direction (TD) secant modulus at about 1% strain of fromabout 170 MPa to about 280 MPa. In another embodiment of the invention,a ˜1 mil film will have a transverse direction (TD) secant modulus atabout 1% strain of from about 180 MPa to about 300 MPa. In anotherembodiment of the invention, a ˜1 mil film will have a transversedirection (TD) secant modulus at about 1% strain of from about 180 MPato about 290 Mpa. In yet another embodiment of the invention, a ˜1 milfilm will have a transverse direction (TD) secant modulus at about 1%strain of from about 190 MPa to about 300 MPa. In another embodiment ofthe invention, a ˜1 mil film will have a transverse direction (TD)secant modulus at about 1% strain of from about 190 MPa to about 290MPa. In another embodiment of the invention, a ˜1 mil film will have atransverse direction (TD) secant modulus at about 1% strain of fromabout 200 MPa to about 290 MPa.

The film or film layer may, by way of non-limiting example only, have atotal thickness ranging from about 0.5 mils to about 4 mils (note: 1mil=0.0254 mm), which will depend on for example the die gap employedduring film casting or film blowing.

The above description applies to monolayer films. However, the film mayalso be used in a multilayer film. Multilayer films can be made using aco-extrusion process or a lamination process. In co-extrusion, aplurality of molten polymer streams are fed to an annular die (or flatcast) resulting in a multi-layered film on cooling. In lamination, aplurality of films are bonded together using, for example, adhesives,joining with heat and pressure and the like. A multilayer film structuremay, for example, contain tie layers and/or sealant layers.

The film of some embodiments the current invention may be a skin layeror a core layer and can be used in at least one or a plurality of layersin a multilayer film. The term “core” or the phrase “core layer”, refersto any internal film layer in a multilayer film. The phrase “skin layer”refers to an outermost layer of a multilayer film (for example, as usedin the production of produce packaging). The phrase “sealant layer”refers to a film that is involved in the sealing of the film to itselfor to another layer in a multilayer film. A “tie layer” refers to anyinternal layer that adheres two layers to one another.

By way of example only, the thickness of the multilayer films can befrom about 0.5 mil to about 10 mil total thickness.

The films can be used for heavy duty bags, shrink film, agriculturalfilm, garbage bags and shopping bags. The films can be produced by blowextrusion, cast extrusion, co-extrusion and be incorporated also inlaminated structures.

The present invention will further be described by reference to thefollowing examples. The following examples are merely illustrative ofthe invention and are not intended to be limiting. Unless otherwiseindicated, all percentages are by weight unless otherwise specified.

EXAMPLES General

All reactions involving air and or moisture sensitive compounds wereconducted under nitrogen using standard Schlenk and cannula techniques,or in a glovebox. Reaction solvents were purified either using thesystem described by Pangborn et. al. in Organometallics 1996, v15, p.1518 or used directly after being stored over activated 4 Å molecularsieves. The methylaluminoxane used was a 10% MAO solution in toluenesupplied by Albemarle which was used as received. The support used wassilica Sylopol 2408 obtained from W.R. Grace. & Co. The support wascalcined by fluidizing with air at 200° C. for 2 hours followed bynitrogen at 600° C. for 6 hours and stored under nitrogen.

Melt index, I₂, in g/10 min was determined on a Tinius Olsen Plastomer(Model MP993) in accordance with ASTM D1238 Procedure A (ManualOperation) at 190° C. with a 2.16 kilogram weight. Melt index, I₁₀, wasdetermined in accordance with ASTM D1238 Procedure A at 190° C. with a10 kilogram weight. High load melt index, I₂₁, in g/10 min wasdetermined in accordance with ASTM D1238 Procedure A at 190° C. with a21.6 kilogram weight. Melt flow ratio (also sometimes called melt indexratio) is I₂₁/I₂.

Polymer density was determined in grams per cubic centimeter (g/cc)according to ASTM D792.

Molecular weight information (M_(w), M_(n) and M_(z) in g/mol) andmolecular weight distribution (M_(w)/M_(n)), and z-average molecularweight distribution (M_(z)/M_(w)) were analyzed by gel permeationchromatography (GPC), using an instrument sold under the trade name“Waters 150c”, with 1,2,4-trichlorobenzene as the mobile phase at 140°C. The samples were prepared by dissolving the polymer in this solventand were run without filtration. Molecular weights are expressed aspolyethylene equivalents with a relative standard deviation of 2.9% forthe number average molecular weight (“Mn”) and 5.0% for the weightaverage molecular weight (“Mw”). Polymer sample solutions (1 to 2 mg/mL)were prepared by heating the polymer in 1,2,4-trichlorobenzene (TCB) androtating on a wheel for 4 hours at 150° C. in an oven. The antioxidant2,6-di-tert-butyl-4-methylphenol (BHT) was added to the mixture in orderto stabilize the polymer against oxidative degradation. The BHTconcentration was 250 ppm. Sample solutions were chromatographed at 140°C. on a PL 220 high-temperature chromatography unit equipped with fourShodex columns (HT803, HT804, HT805 and HT806) using TCB as the mobilephase with a flow rate of 1.0 mL/minute, with a differential refractiveindex (DRI) as the concentration detector. BHT was added to the mobilephase at a concentration of 250 ppm to protect the columns fromoxidative degradation. The sample injection volume was 200 mL. The rawdata were processed with Cirrus GPC software. The columns werecalibrated with narrow distribution polystyrene standards. Thepolystyrene molecular weights were converted to polyethylene molecularweights using the Mark-Houwink equation, as described in the ASTMstandard test method D6474.

The branch frequency of copolymer samples (i.e. the short chainbranching, SCB per 1000 carbons) and the C₆ comonomer content (in wt %)was determined by Fourier Transform Infrared Spectroscopy (FTIR) as perthe ASTM D6645-01 method. A Thermo-Nicolet 750 Magna-IRSpectrophotometer equipped with OMNIC version 7.2a software was used forthe measurements.

The determination of branch frequency as a function of molecular weight(and hence the comonomer distribution) was carried out using hightemperature Gel Permeation Chromatography (GPC) and FT-IR of the eluent.Polyethylene standards with a known branch content, polystyrene andhydrocarbons with a known molecular weight were used for calibration.

Hexane extractables using compression molded plaques were determinedaccording to ASTM D5227.

To determine the composition distribution breadth index CDBI₅₀ (which isalso designated CDBI(50)—CDBI₅₀ and CDBI(50) are used interchangeablyherein), a solubility distribution curve is first generated for thecopolymer. This is accomplished using data acquired from the TREFtechnique (see below). This solubility distribution curve is a plot ofthe weight fraction of the copolymer that is solubilized as a functionof temperature. This is converted to a cumulative distribution curve ofweight fraction versus comonomer content, from which the CDBI₅₀ isdetermined by establishing the weight percentage of a copolymer samplethat has a comonomer content within 50% of the median comonomer contenton each side of the median (see WO 93/03093 for the definition ofCDBI₅₀). The weight percentage of copolymer eluting at from 90-105° C.,is determined by calculating the area under the TREF curve at an elutiontemperature of from 90 to 105° C. The weight percent of copolymereluting below at or 40° C. and above 100° C. was determined similarly.For the purpose of simplifying the correlation of composition withelution temperature, all fractions are assumed to have a Mn≧15,000,where Mn is the number average molecular weight of the fraction. Any lowweight fractions present generally represent a trivial portion of thepolymer. The remainder of this description and the appended claimsmaintain this convention of assuming all fractions have Mn≧15,000 in theCDBI₅₀ measurement.

The specific temperature rising elution fractionation (TREF) method usedherein was as follows. Homogeneous polymer samples (pelletized, 50 to150 mg) were introduced into the reactor vessel of acrystallization-TREF unit (Polymer ChAR™). The reactor vessel was filledwith 20 to 40 mL 1,2,4-trichlorobenzene (TCB), and heated to the desireddissolution temperature (e.g. 150° C.) for 1 to 3 hours. The solution(0.5 to 1.5 mL) was then loaded into the TREF column filled withstainless steel beads. After equilibration at a given stabilizationtemperature (e.g. 110° C.) for 30 to 45 minutes, the polymer solutionwas allowed to crystallize with a temperature drop from thestabilization temperature to 30° C. (0.1 or 0.2° C./minute). Afterequilibrating at 30° C. for 30 minutes, the crystallized sample waseluted with TCB (0.5 or 0.75 mL/minute) with a temperature ramp from 30°C. to the stabilization temperature (0.25 or 1.0° C./minute). The TREFcolumn was cleaned at the end of the run for 30 minutes at thedissolution temperature. The data were processed using Polymer ChARsoftware, Excel spreadsheet and TREF software developed in-house.

The TREF procedures described above are well known to persons skilled inthe art and can be used to determine the modality of a TREF profile, aCDBI₅₀, a copolymer wt % eluting at or below 40° C., a copolymer wt %eluting at above 100° C., a copolymer wt % eluting at from 90° C. to105° C., a T(75)−T(25) value, as well as the temperatures or temperatureranges where elution intensity maxima (elution peaks) occur.

The melting points including a peak melting point (T_(m)) and thepercent crystallinity of the copolymers are determined by using a TAInstrument DSC Q1000 Thermal Analyzer at 10° C./min. In a DSCmeasurement, a heating-cooling-heating cycle from room temperature to200° C. or vice versa is applied to the polymers to minimize thethermo-mechanical history associated with them. The melting point andpercent of crystallinity are determined by the primary peak temperatureand the total area under the DSC curve respectively from the secondheating data. The peak melting temperature T_(m) is the highertemperature peak, when two peaks are present in a bimodal DSC profile(typically also having the greatest peak height).

The melt strength of a polymer is measured on Rosand RH-7 capillaryrheometer (barrel diameter=15 mm) with a flat die of 2-mm Diameter, L/Dratio 10:1 at 190° C. Pressure Transducer: 10,000 psi (68.95 MPa).Piston Speed: 5.33 mm/min. Haul-off Angle: 52°. Haul-off incrementalspeed: 50-80 m/min² or 65±15 m/min². A polymer melt is extruded througha capillary die under a constant rate and then the polymer strand isdrawn at an increasing haul-off speed until it ruptures. The maximumsteady value of the force in the plateau region of a force versus timecurve is defined as the melt strength for the polymer.

Dynamic Mechanical Analysis (DMA). Rheological measurements (e.g.small-strain (10%) oscillatory shear measurements) were carried out on adynamic Rheometrics SR5Stress rotational rheometer with 25 mm diameterparallel plates in a frequency sweep mode under full nitrogenblanketing. The polymer samples are appropriately stabilized with theanti-oxidant additives and then inserted into the test fixture for atleast one minute preheating to ensure the normal force decreasing backto zero. All DMA experiments are conducted at 10% strain, 0.05 to 100rad/s and 190° C. Orchestrator Software is used to determine theviscoelastic parameters including the storage modulus (G′), loss modulus(G″), phase angle (δ), complex modulus (G*) and complex viscosity (η*).

The complex viscosity |η*(ω)| versus frequency (ω) data were then curvefitted using the modified three parameter Carreau-Yasuda (CY) empiricalmodel to obtain the zero shear viscosity η₀, characteristic viscousrelaxation time τ_(η), and the breadth of rheology parameter-a. Thesimplified Carreau-Yasuda (CY) empirical model used is as follows:

|η*(ω)|=η₀/[1+(τ_(η)ω)^(a)]^((1-n)/a)

wherein: |η*(ω)|=magnitude of complex shear viscosity; η₀=zero shearviscosity; τ_(η) characteristic relaxation time; a=“breadth” of rheologyparameter (which is also called the “Carreau-Yasuda shear exponent” orthe “CY a-parameter” or simply the “a-parameter”); n=fixes the finalpower law slope, fixed at 2/11; and ω=angular frequency of oscillatoryshearing deformation. Details of the significance and interpretation ofthe CY model and derived parameters may be found in: C. A. Hieber and H.H. Chiang, Rheol. Acta, 28, 321 (1989); C. A. Hieber and H. H. Chiang,Polym. Eng. Sci., 32, 931 (1992); and R. B. Bird, R. C. Armstrong and O.Hasseger, Dynamics of Polymeric Liquids, Volume 1, Fluid Mechanics, 2ndEdition, John Wiley & Sons (1987); each of which is incorporated hereinby reference in its entirety.

The Shear Thinning Index (SHI) was determined according to the methodprovided in U.S. Pat. Appl. No. 2011/0212315: the SHI is defined asSHI(ω)=η*(ω)/η0 for any given frequency (ω) for dynamic viscositymeasurement, wherein η0 is zero shear viscosity @190° C. determined viathe empiric Cox-Merz-rule. η* is the complex viscosity @190° C.determinable upon dynamic (sinusoidal) shearing or deformation of acopolymer as determined on a Rheometrics SR5Stress rotational rheometerusing parallel-plate geometry. According to the Cox-Merz-Rule, when thefrequency (ω) is expressed in Radiant units, at low shear rates, thenumerical value of η* is equal to that of conventional, intrinsicviscosity based on low shear capillary measurements. The skilled personin the field of rheology is well versed with determining η0 in this way.

The films of the current examples were made on a blown film linemanufactured by Battenfeld Gloucester Engineering Company of Gloucester,Mass. using a die diameter of 4 inches, and a die gap of 35 or 50 mil(note: a fluoroelastomer type PPA was added to inv. resin 1 for purposesof film production; analysis of competitive resin 2 shows that ca.250-300 ppm of a fluoroelatomer PPA is present; analysis of competitiveresin 3 suggests ca. 600 ppm of carbowax and fluoroelatomer PPA in totalis present). This blown film line has a standard output of more than 100pounds per hour and is equipped with a 50 horsepower motor. Screw speedwas 35 to 50 RPM. The extender screw has a 2.5 mil diameter and alength/diameter (L/D) ratio of 24/1. Melt Temperature and Frost LineHeight (FLH) are 420 to 430° F. and 16 inches respectively. The blownfilm bubble is air cooled. Typical blow up ratio (BUR) for blown filmsprepared on this line are from 1.5/1 to 4/1. An annular die having a gapof 35 mils was used for these experiments. The films of this examplewere prepared using a BUR aiming point of 2.5:1 and a film thicknessaiming point of 1.0 mils.

The haze (%) was measured in accordance with the procedures specified inASTM D 1003-07, using a BYK-Gardner Haze Meter (Model Haze-gard plus).

Dart impact strength was measured on a dart impact tester (ModelD2085AB/P) made by Kayeness Inc. in accordance with ASTM D-1709-04(method A).

Machine (MD) and transverse (TD) direction Elmendorf tear strengths weremeasured on a ProTear™ Tear Tester made by Thwing-Albert Instrument Co.in accordance with ASTM D-1922.

Puncture resistance was measured on a MTS Systems Universal Tester(Model SMT(HIGH)-500N-192) in accordance with ASTM D-5748.

MD or TD secant modulus was measured on an Instrument 5-Head UniversalTester (Model TTC-102) at a crosshead speed of 0.2 in/min up to 10%strain in accordance with ASTM D-882-10. The MD or TD secant modulus wasdetermined by an initial slope of the stress-strain curve from an originto 1% strain.

Film tensile testing was conducted on an Instrument 5-Head UniversalTester (Model TTC-102) in accordance with ASTM D-882-10.

Gloss was measured on a BYK-Gardner 45° Micro-Gloss unit in accordancewith ASTM D2457-03.

A seal was prepared by clamping two 2.0 mil film strips between heatedupper and lower seal bars on a SL-5 Sealer made by Lako Tool for 0.5seconds, 40 psi seal bar clamping pressure for each temperature in therange from onset of seal to melt through. Seal strength or sealabilityparameter was measured as a function of seal temperature on anInstrument 5-Head Universal Tester (Model TTC-102) in accordance withASTM F88-09.

Inventive Examples Catalyst System Preparation Synthesis of(1-C₆F₅CH₂-Indenyl)((t-Bu)₃P═N)TiCl₂

To distilled indene (15.0 g, 129 mmol) in heptane (200 mL) was addedBuLi (82 mL, 131 mmol, 1.6 M in hexanes) at room temperature. Theresulting reaction mixture was stirred overnight. The mixture wasfiltered and the filter cake washed with heptane (3×30 mL) to giveindenyllithium (15.62 g, 99% yield). Indenyllithium (6.387 g, 52.4 mmol)was added as a solid over 5 minutes to a stirred solution of C₆F₅CH₂—Br(13.65 g, 52.3 mmol) in toluene (100 mL) at room temperature. Thereaction mixture was heated to 50° C. and stirred for 4 h. The productmixture was filtered and washed with toluene (3×20 mL). The combinedfiltrates were evaporated to dryness to afford 1-C₆F₅CH₂-indene (13.58g, 88%). To a stirred slurry of TiCl₄.2THF (1.72 g, 5.15 mmol) intoluene (15 mL) was added solid (t-Bu)₃P═N—Li (1.12 g, 5 mmol) at roomtemperature. The resulting reaction mixture was heated at 100° C. for 30min and then allowed to cool to room temperature. This mixturecontaining ((t-Bu)₃P═N)TiCl₃ (1.85 g, 5 mmol) was used in the nextreaction. To a THF solution (10 mL) of 1-C₆F₅CH₂-indene (1.48 g, 5 mmol)cooled at −78° C. was added n-butyllithium (3.28 mL, 5 mmol, 1.6 M inhexanes) over 10 minutes. The resulting dark orange solution was stirredfor 20 minutes and then transferred via a double-ended needle to atoluene slurry of ((t-Bu)₃P═N)TiCl₃ (1.85 g, 5 mmol). The cooling wasremoved from the reaction mixture which was stirred for a further 30minutes. The solvents were evaporated to afford a yellow pasty residue.The solid was re-dissolved in toluene (70 mL) at 80° C. and filteredhot. The toluene was evaporated to afford pure(1-C₆F₅CH₂-Indenyl)((t-Bu)₃P═N)TiCl₂ (2.35 g, 74%).

Drying of the Catalyst Modifier.

950 g of commercially available Armostat® 1800 (mp 50° C., by >300° C.),which was used as a catalyst modifier, was loaded in a 2 L-round bottomflask and melted in an oil bath at 80° C. The oil bath temperature wasthen raised to 110° C. and a high vacuum was applied while maintainingstirring. At first, a lot of bubbles were seen due to the release of gasand moisture vapor. Approximately two hours later, gas evolutionsubsided and heating/evacuation was continued for another hour. TheArmostat 1800 material was then cooled down to room temperature andstored under nitrogen atmosphere until use.

To determine the level of moisture in the Armostat 1800, a 15 wt % of anArmostat solution in pre-dried toluene was prepared and the moisture ofthe solution was determined by Karl-Fischer titration method. Themoisture levels in Armostat 1800 as received from the commercialsupplier, as well as that dried by traditional methods (i.e. drying thesolution over molecular sieves) and by use of low pressure waterdistillation was determined. The unpurified catalyst modifier was foundto make a 15 wt % toluene solution having 138 ppm of H₂O. The catalystmodifier which was dried over molecular sieves was found to make a 15 wt% toluene solution having 15-20 ppm of H₂O. The catalyst modifier whichwas dried by vacuum distillation of water was found to make a 15 wt %toluene solution having 14-16 ppm of H₂O. It has thus been shown, thatsimple vacuum distillation to remove water is as effective as dryingmethods which employ molecular sieves. In fact, the vacuum distillationhas an advantage over use of molecular sieves as a drying agent in thatit is far less time consuming (molecular sieves took over 2 days to drythe catalyst modifier sufficiently and multiple batches of the sieveswere used), and more cost effective (the use of sieves led to a decreasein the concentration of the catalyst modifier in toluene solution due tocatalyst modifier absorption into the sieves, and used large quantitiesof solvent to sufficiently solubilize the catalyst modifier in order tomake efficient contact with the sieves).

Preparation of Supported Catalyst.

Sylopol 2408 silica purchased from Grace Davison was calcined byfluidizing with air at 200° C. for 2 hours and subsequently withnitrogen at 600° C. for 6 hours. 114.273 grams of the calcined silicawas added to 620 mL of toluene. 312.993 g of a MAO solution containing4.5 weight % Al purchased from Albemarle was added to the silica slurryquantitatively. The mixture was stirred for 2 hours at ambienttemperature. The stirring rate should be such so as not to break-up thesilica particles. 2.742 grams of (1-C₆F₅CH₂-Indenyl)((t-Bu)₃P═N)TiCl₂(prepared as above in Example 1) was weighed into a 500-mL Pyrex bottleand 300 mL of toluene added. The metal complex solution was added to thesilica slurry quantitatively. The resulting slurry was stirred for 2hours at ambient temperature. 21.958 g of 18.55 wt % toluene solution ofArmostat® 1800 was weighed into a small vessel and transferredquantitatively to the silica slurry. The resulting mixture was stirredfor a further 30 minutes after which the slurry was filtered, yielding aclear filtrate. The solid component was washed with toluene (2×150 mL)and then with pentane (2×150 mL). The final product was dried in vacuoto between 450 and 200 mtorr and stored under nitrogen until used. Thefinished catalyst had a pale yellow to pale orange colour. The catalysthad 2.7 wt % of Armostat present.

Polymerization—TSR

Continuous ethylene/1-hexene gas phase copolymerization experiments wereconducted in a 56.4 L Technical Scale Reactor (TSR) in continuous gasphase operation (for an example of a TSR reactor set up see Eur. Pat.Appl. No. 659,773A1). Ethylene polymerizations were run at 75° C.-90° C.with a total operating pressure of 300 pounds per square inch gauge(psig). Gas phase compositions for ethylene and 1-hexene were controlledvia closed-loop process control to values of 65.0 and 0.5-2.0 mole %,respectively. Hydrogen was metered into the reactor in a molar feedratio of 0.0008-0.0020 relative to ethylene feed during polymerization.Nitrogen constituted the remainder of the gas phase mixture(approximately 34-64 mole %). A typical production rate for theseconditions is 2.0 to 3.0 kg of polyethylene per hour. A seed-bed wasused and prior to polymerization start-up was washed with a small amountof triethylaluminum, TEAL to scavenge impurities. Prior to introductionof the catalyst TEAL was flushed from the reactor. The catalyst was fedto the reactor together with small amount of dilute TEAL solution (0.25wt %) during the start-up phase. The addition of TEAL was discontinuedonce the desired polymer production rate was reached. Alternatively, thereactor can be started with the catalyst feed line alone during thepolymerization start-up phase (that is, without initially feeding theTEAL solution). The polymerization reaction was initiated underconditions of low comonomer concentration, followed by gradualadjustment of the comonomer to ethylene ratio to provide the targetedpolymer density.

Pelletization of Granular Resins.

500 ppm of Irganox 1076 and 1000 ppm of Irgafos 168 were dry blendedwith the granular resin prior to pelletization. The resulting powderblend was extruded on Leistritz twin-screw extruder with a screwdiameter of 38 mm and L/D ratio of 33/1 under nitrogen atmosphere tominimize polymer degradation. The pelletization conditions of theextruder were set at a melt temperature of 210° C. an output rate of 20to 25 lb/hr, a screw speed of 120 rpm and a pelletizer speed of 30 to 40rpm. The pelleted resin was cooled and then collected for the resincharacterization and film evaluation.

Catalyst composition information and steady state polymerizationconditions are provided in Table 1 (C2=ethylene; C6=1-hexene;H2=hydrogen; and C6/C2 for example is the molar feed ratio of eachcomponent to the reactor). Polymer data for the resulting inventiveresins are provided in Table 2. Film data for inventive films made fromthe inventive resins are provided in Table 3.

Polymerization-Pilot Plant

Ethylene/1-hexene copolymerization experiments were conducted in acontinuous fluidized bed gas phase Pilot Plant scale reactor. An exampleof a reactor configuration and typical process operational parameters isgiven in for example U.S. Pat. No. 8,338,551 B2 and in Eur. Pat. Appl.No. 1,308,464 A1 (see Examples 10 and 11). Ethylene polymerizations wererun at 80° C.-85° C. with a total operating pressure of 300 pounds persquare inch gauge (psig). Gas phase compositions for ethylene and1-hexene were controlled via closed-loop process control to values of35-50.0 and 0.5-2.0 mole %, respectively. Hydrogen was metered into thereactor in a molar feed ratio of 0.0008-0.0015 relative to ethylene feedduring polymerization. Nitrogen constituted the remainder of the gasphase mixture (approximately 34-49 mole %). A typical production ratefor these conditions is 100 to 250 kg of polyethylene per hour. Aseed-bed was used and prior to polymerization start-up was washed with asmall amount of triethylaluminum, TEAL to scavenge impurities. The gascomposition of ethylene, 1-hexene, hydrogen, nitrogen andpentane/isopentane in the reactor is built to target amounts beforeinjection of catalyst. The level of pentane/isopentane can range from9-17 mole % in the reactor. The reactor was started with the catalystfeed line alone without additional scavenging with TEAL during thepolymerization start-up. The polymerization reaction was initiated underconditions of lower comonomer concentration and higher hydrogenconcentration, followed by gradual adjustment of the comonomer toethylene ratio and hydrogen to ethylene ratio to achieve targetedpolymer density and melt index. Pelletization of the granular resin wascarried out as per TSR scale (see above).

Catalyst composition information and steady state polymerizationconditions are provided in Table 1 (C2=ethylene; C6=1-hexene;H2=hydrogen; and C6/C2 for example is the molar feed ratio of eachcomponent to the reactor). Polymer data for the resulting inventiveresins are provided in Table 2. Film data for inventive films made fromthe inventive resins are provided in Table 3.

TABLE 1 TSR Pilot Plant Example No. Inv. 1 Inv. 2 Inv. 3 Inv. 4 Inv. 5Inv. 6 Catalyst Ti, wt % 0.14 0.12 0.12 0.134 0.134 0.134 Al, wt % 9.4 77 7.86 7.86 7.86 Si, wt % 35.5 38.3 37.8 37.3 37.3 37.3 Armostat, wt %2.7 2.5 2.5 2.5 2.5 2.5 Process Productivity (g PE/g 3400 1300 2480 36755656 5339 Cat) Ethylene (mole %) 50 56 39 45 46 44 Hydrogen (mol %)0.035 0.034 0.029 0.027 0.032 0.032 1-Hexene (mol %) 0.8603 0.95860.6903 0.8562 0.8049 0.7671 C6/C2 (mol/mol feed 0.0232 0.0215 0.02510.0260 0.0260 0.0260 to reactor) H2/C2 (mol/mol feed 0.0013 0.00130.0015 0.0015 0.0019 0.0019 to reactor) H2/C2 in reactor 0.00070 0.000620.00075 0.00060 0.00070 0.00073 (mol/mol Gas composition) C6/C2 inreactor 0.0172 0.0173 0.0176 0.0190 0.0175 0.0175 (mol/mol Gascomposition) Temp (° C.) 80 80 82.5 82.5 80.0 82.5 Production rate 2.582.46 180 172 202 202 (kg/hr) Residence Time (hrs) 1.8 1.8 2.6 2.0 2.42.5 Bulk Density (lb per 22.5 19.5 20.6 24.5 28.2 26.1 cubic foot)Isopentane and 0 11 17 11 12 11 Pentane in reactor, (mole %) TEAL asscavenger yes No no no no no

TABLE 2 Copolymer Properties Copolymer No. Inv. 1 Inv. 2 Inv. 3 Inv. 4Inv. 5 Inv. 6 density (g/cc) 0.9208 0.922 0.9226 0.9214 0.9224 0.9228MI, I₂ (g/10 min) 0.58 0.53 0.49 0.57 0.56 1.22 MFR, I₂₁/I₂ 44.5 42.735.3 37.8 43 35.3 I₁₀/I₂ 10.9 10.6 9.45 9.67 10.3 9.1 Comonomer 1-hexene1-hexene 1-hexene 1-hexene 1-hexene 1-hexene TREF profile trimodal,multimodal, multimodal, multimodal, multimodal, multimodal, T(low) =T(high) = T(high) = T(high) = T(high) = T(high) = 71.5° C.; 93.6° C.;93.3° C.; 93.1° C.; 93.2° C.; 93.1° C.; T(med) = T(low) = T(low) =T(low) = T(low) = T(low) = 81.3° C.; 73.6° C. 78.5° C. 73.4° C. 74.4° C.74.9° C. T(high) = 92.3° C. T(med) − T(low), ° C. 9.8 — — — — — T(high)− T(med), ° C. 11.0 — — — — — T(high) − T(low), ° C. 20.2 20.0 14.8 19.718.8 18.2 wt % at 90-105° C. 12.9 15.4 15.9 15.1 14.6 13.9 T(75) − T(25)(° C.) 14.4 13.75 9.5 13.7 13.3 13 CDBI₅₀ (wt %) 65.6 64.1 71.7 64.265.1 64.9 comonomer profile reverse reverse reverse reverse reversereverse DSC melt temp (° C.) 104.2, 120.3 106.4, 121.1 109.3, 120.4107.2, 120.9 106.6, 120.7 108.5, 120.5 % crystallinity 46.1 46.8 49.146.6 48.3 48.7 CY a-parameter 0.0947 0.1228 0.1229 0.2622 0.2320 0.2221M_(n) 20.3 × 10³ 24228 24783 25646 20438 20022 M_(w) 97.3 × 10³ 120830118772 126052 121308 103207 M_(z) 226.4 × 10³  355544 334655 374146359545 313009 M_(w)/M_(n) 4.78 4.99 4.79 4.92 5.94 5.15 M_(z)/M_(w) 2.332.94 2.82 2.97 2.96 3.03 C₆ content (wt %) 7.3 6.8 6.0 6.8 6.8 6.5SCB/1000 C 12.7 11.8 10.4 11.8 11.9 11.3 hexane extractables (wt %) 0.940.89 0.52 0.80 0.90 0.90 melt strength (cN) 5.74 6.39 8.27 6.27 6.003.81 VGP crossover phase angle 59.6 62.81 60.45 64.74 62.01 67.43(δ^(XO)) SCB/1000C at MW of 200,000 − 6.1 6.6 3.8 5.9 5.9 5.3 SCB/1000Cat MW of 50,000 Shear Thinning Index (SHI) 0.015 0.123 0.065 0.459 0.3430.429 83.0 − 1.25 (CDBI₅₀)/(M_(w)/M_(n)) 65.85 66.94 64.29 66.69 69.3067.25 80.7 − (CDBI₅₀)/(M_(w)/M_(n)) 66.98 67.85 65.79 67.65 69.74 68.1072 [(I₂₁/I₂)⁻¹ + 10⁻⁶ (M_(n))] 3.08 3.43 3.82 3.75 3.15 3.48

TABLE 3 Film Properties Film No. Inv. 1 Inv. 2 Inv. 3 Inv. 4 Inv. 5 Inv.6 die gap (mils) 35 50 35 35 35 35 film gauge (mils) 1 1 1 1 1 1 dartimpact (g/mil) 638 438 887 542 684 225 puncture strength (J/mm) 53 57 5244 44 48 MD tear (g/mil) 121 67 84 80 79 115 TD tear (g/mil) 455 493 405446 455 501 1% MD secant modulus (Mpa) 198 148 228 206 221 230 1% TDsecant modulus (MPa) 220 264 275 260 263 255 MD tensile strength (MPa)51.0 51.6 55.3 52.2 55.2 49.6 TD tensile strength (MPa) 48.8 42.5 52.047.6 44.6 41.8 MD yield strength (MPa) 10.9 12.2 11.6 11.5 11.5 11.6 TDyield strength (MPa) 11.2 11.7 11.8 12.0 11.8 12.1 MD ultimateelongation (%) 477 479 483 514 501 567 TD ultimate elongation (%) 696677 682 695 684 731 gloss at 45° (%) 50 41 40.8 35 35 50 haze (%) 11.214.8 14.5 16.2 17.2 11.2 Sealability on 2.0 mil Films: seal initiationtemp. (° C.) 112 115 112 116 117 117 max. cold seal strength (N) 14.314.8 16.7 16.9 15.8 13.7 temp. at max. seal strength 130 150 150 150 160140 (° C.) Film Processing Parameters: Melt Temp (° F.) 429 422 429 427427 421 Extruder Pressure (psi) 3450-3495 2975 4055 3729 3693 2953Current (amp) 36 33 40 36 36 31 Voltage (V) 190 176 193 189 191 181spec. output (lb/hr/rpm) 2.50 2.70 2.50 2.50 2.50 2.63 Specific energy(w/lb/hr) 68.4 58.1 77.2 68.0 68.8 56.1 PPA additive (ppm) 650 400 750750 750 750

COMPARATIVE EXAMPLES Comparative Example 1 Catalyst System Preparation

The phosphinimine catalyst compound(1,2-(n-propyl)(C₆F₅)Cp)Ti(N═P(t-Bu)₃)Cl₂ was made in a manner similarto the procedure given in U.S. Pat. No. 7,531,602 (see Example 2).

Preparation of the Supported Catalyst.

To a slurry of dehydrated silica (122.42 g) in toluene (490 mL) wasadded a 10 wt % MAO solution (233.84 g of 4.5 wt % Al in toluene) over10 minutes. The vessel containing the MAO was rinsed with toluene (2×10mL) and added to the reaction mixture. The resultant slurry was stirredwith an overhead stirrer assembly (200 rpm) for 1 hour at ambienttemperature. To this slurry was added a toluene (46 mL) solution of(1,2-(n-propyl)(C₆F₅)Cp)Ti(N═P(t-Bu)₃)Cl₂ (2.28 g) over 10 minutes. Thissolution may need to be gently heated to 45° C. for a brief period (5minutes) to fully dissolve the molecule. The vessel containing themolecule was rinsed with toluene (2×10 mL) and added to the reactionmixture. After stirring for 2 hours (200 rpm) at ambient temperature atoluene (22 mL) solution of Armostat-1800 (which was previously driedaccording to the method above for “Drying a Catalyst Modifier”) at 8.55wt % was added to the slurry which was further stirred for 30 minutes.The slurry was filtered and rinsed with toluene (2×100 mL) and then withpentane (2×100 mL). The catalyst was dried in vacuo to less than 1.5 wt% residual volatiles. The solid catalyst was isolated and stored undernitrogen until further use. The catalyst had 2.7 wt % of Armostatpresent.

Polymerization

Continuous ethylene/1-hexene gas phase copolymerization experiments wereconducted in a 56.4 L Technical Scale Reactor (TSR) in continuous gasphase operation. Ethylene polymerizations were run at 75° C.-90° C. witha total operating pressure of 300 pounds per square inch gauge (psig).Gas phase compositions for ethylene and 1-hexene were controlled viaclosed-loop process control to values of 65.0 and 0.5-2.0 mole %,respectively. Hydrogen was metered into the reactor in a molar feedratio of 0.0008-0.0015 relative to ethylene feed during polymerization.Nitrogen constituted the remainder of the gas phase mixture(approximately 38 mole %). A typical production rate for theseconditions is 2.0 to 3.0 kg of polyethylene per hour.

Pelletization of Granular Resins.

500 ppm of Irganox 1076 and 1000 ppm of Irgafos 168 were dry blendedwith the granular resin prior to pelletization. The resulting powderblend was extruded on Leistritz twin-screw extruder with a screwdiameter of 38 mm and L/D ratio of 33/1 under nitrogen atmosphere tominimize polymer degradation. The pelletization conditions of theextruder were set at a melt temperature of 210° C. an output rate of 20to 25 lb/hr, a screw speed of 120 rpm and a pelletizer speed of 30 to 40rpm. The pelleted resin was cooled and then collected for the resincharacterization and film evaluation.

Steady state polymerization conditions are provided in Table 4(C2=ethylene; C6=1-hexene; C6/C2 is the molar feed ratio of eachcomponent to the reactor). Polymer data for the resulting comparativeresin 1 is provided in Table 5. Film data for films made from thecomparative resin 1 is provided in Table 6.

TABLE 4 Catalyst Comp. 1 Productivity (g PE/g Cat) 7700 Hydrogen (mol %)0.0298 1-Hexene (mol %) 1.2110 C6/C2 (mol/mol feed) 0.0215 Temp (° C.)85 Production rate (kg/hr) 2.53 Residence Time (hrs) 1.62 Bulk Density(lb per cubic foot) 17.9 Isopentane (weight %) 0

Also included in Table 5 are comparative resins 2-8. Corresponding filmproperties for comparative resins 2-8 are given in Table 6. Comparativeresin 2 is an Exceed 1018CA™ ethylene copolymer of 1-hexene, which iscommercially available from ExxonMobil. Comparative resin 3 is believedto be a resin representative of Enable 20-05™ which is commerciallyavailable from ExxonMobil. Comparative resin 4 is believed to be a resinrepresentative of Enable 20-10™ which is commercially available fromExxonMobil. Comparative resin 5 is a melt blend of FP-019C andLF-Y819-A. LF-Y819 represents 5% by weight of the melt blend. LF-Y819-A,is a high pressure low density material having a melt index I₂ of 0.75g/10 min and a density of 0.919 g/cc, available from NOVA Chemicals.FPs-0,9-C is a linear low density material having a melt index I₂ of 0.8g/10 min and a density of 0.918 g/cc, made using a Ziegler-Nattacatalyst, also available form NOVA Chemicals. Comparative Resins 6 and 7are ELITE 5100G™ and ELITE 5400G™ respectively which are made using adual reactor solution process with a mixed catalyst system and arecommercially available from the Dow Chemical Company. Comparative resin8 is DOWLEX 2045G™, which is made with a Ziegler-Natta catalyst in asolution reactor, and is also commercially available from the DowChemical Company.

TABLE 5 Copolymer Properties Copolymer No. Comp. 1 Comp. 2 Comp. 3 Comp.4 density (g/cc) 0.9171 0.9189 0.9203 0.9191 MI, I₂ (g/10 min) 0.90 1.00.47 1.12 MFR, I₂₁/I₂ 16.0 16.2 41.2 32.9 I₁₀/I₂ 5.76 5.76 10.8 9.45Comonomer 1-hexene 1-hexene 1-hexene 1-hexene TREF profile bimodalbimodal single peak at single peak at T(low) = T(low) = T = 81.5° C. T =79.5° C. 80.8° C. 81.4° C. T(high) = T(high) = 91.6° C. 92.9° C. T(med)− T(low), ° C. NA NA NA NA T(high) − T(med), ° C. NA NA NA NA T(high) −T(low), ° C. 10.8 11.5 NA NA wt % at 90-105° C. 10.8 10.9 0.6 0.3 T(75)− T(25) (° C.) 9.3 10.0 4.8 5.8 CDBI₅₀ (wt %) 75.5 70.8 86.8 85.3comonomer profile slightly reverse reverse approx. flat slightlynegative DSC melt temp (° C.) 108.3, 116.9 107.9, 118.8 111.7 113.4 %crystallinity 43.7 45.1 43.8 44.9 CY a-parameter 0.7314 0.7266 0.06160.1543 M_(w) (×10⁻³) 105.3 103.8 96 75.1 M_(n) (×10⁻³) 59.6 53.1 31.4 25M_(z) (×10⁻³) 167.4 167.4 193 143.1 M_(w)/M_(n) 1.77 1.96 3.05 3.01M_(z)/M_(w) 1.59 1.61 2.0 1.90 C₆ content (wt %) 5.9 6.3 6.5 6.8SCB/1000 C 10.2 10.9 11.3 11.9 hexane extractables (wt %) 0.18 0.32 0.390.44 melt strength (cN) 3.43 2.56 5.93 3.71 VGP crossover phase angle82.1 84.2 54.3 65.7 (δ^(XO)) SCB/1000C at MW of 200,000 − 1.9 1.6 −0.2(or <0) −0.47 (or <0) SCB/1000C at MW of 50,000 Shear Thinning Index(SHI) 0.99 0.99 <0.01 0.20 83.0 − 1.25 (CDBI₅₀)/(M_(w)/M_(n)) 29.6837.84 47.43 47.58 80.7 − (CDBI₅₀)/(M_(w)/M_(n)) 38.05 44.58 52.24 52.3672 [(I₂₁/I₂)⁻¹ + 10⁻⁶ (M_(n))] 8.79 8.27 4.01 3.99 Copolymer No. Comp. 5Comp. 6 Comp. 7 Comp. 8 density (g/cc) 0.9192 0.9204 0.9164 0.9182 MI,I₂ (g/10 min) 0.67 0.82 1.00 0.98 MFR, I₂₁/I₂ 32.1 24 32.0 28.2 I₁₀/I₂8.7 7.08 8.55 7.97 Comonomer 1-hexene 1-octene 1-octene 1-octene TREFprofile bimodal trimodal trimodal bimodal T(low) = T(low) = T(low) =T(low) = 77.4° C. 66.8° C. 66.1° C. 80.0° C. T(high) = T(med) = T(med) =T(high) = 94.6° C. 84.3° C. 83.5° C. 93.8° C. T(high) = T(high) = 95.4°C. 94.6° C. T(med) − T(low), ° C. NA 17.5 17.4 NA T(high) − T(med), ° C.NA 11.1 11.1 NA T(high) − T(low), ° C. 17.2 28.6 28.5 13.8 wt % at90-105° C. 13.7 23.3 14.7 18.2 T(75) − T(25) (° C.) 16.0 23.3 20.1 15.7CDBI₅₀ (wt %) 58.2 35.2 55.7 54.0 comonomer profile normal reversereverse normal DSC melt temp (° C.) 107.8, 119.5 94.5, 124.4 100.5,117.9, 122.5 109.9, 118.4, 121.8 % crystallinity 42.4 46.2 41.9 43.1 CYa-parameter — 0.4239 0.2666 0.4229 M_(w) (×10⁻³) 115.3 99.5 94.4 94.0M_(n) (×10⁻³) 42.1 39.9 36.5 26.7 M_(z) (×10⁻³) 421 196.1 192.2 24.5M_(w)/M_(n) 2.74 2.49 2.59 3.52 M_(z)/M_(w) 3.65 1.97 2.03 2.61 C₆content (wt %) — 2.6 11.1 9.8 SCB/1000 C — 3.3 15.2 13.2 hexaneextractables (wt %) — 0.32 0.52 0.64 melt strength (cN) — 3.29 4.14 3.24VGP crossover phase angle — 76.65 70.81 73.97 (δ^(XO)) SCB/1000C at MWof 200,000 − — 3.9 4.0 −2.2 SCB/1000C at MW of 50,000 Shear ThinningIndex (SHI) — 0.87 0.60 0.84 83.0 − 1.25 (CDBI₅₀)/(M_(w)/M_(n)) 56.4565.33 56.12 63.82 80.7 − (CDBI₅₀)/(M_(w)/M_(n)) 59.46 66.56 59.19 65.3672 [(I₂₁/I₂)⁻¹ + 10⁻⁶ (M_(n))] 5.27 5.87 4.89 4.48

TABLE 6 Film Properties Film No. Comp. 2 Comp. 3 Comp. 4 Comp. 5 Die gap(mils) 35 35 35 35 Die film gauge (mils) 1 1 1 1 dart impact (g/mil) 650473 286 317 puncture strength (J/mm) 71 63 55 57 MD tear (g/mil) 257 107147 234 TD tear (g/mil) 405 448 461 629 1% MD secant modulus 137 187 156167 (Mpa) 1% TD secant modulus 166 208 171 208 (MPa) MD tensile strength56.6 49.9 53.8 51.6 (MPa) TD tensile strength 41.0 49.3 43 47.1 (MPa) MDyield strength (MPa) 9.1 10.4 9.8 10.2 TD yield strength (MPa) 9.2 10.99.7 10.0 MD ultimate elongation 571 476 593 469 (%) TD ultimateelongation 654 712 728 770 (%) gloss at 45° (%) 68 60 61 72 haze (%) 7.27.7 8.4 5.2 Sealability on 2.0 mil Films: seal initiation temp. 103 111108 103 (° C.) max. cold seal strength 9.8 15.5 15.7 14.1 (N) temp. atmax. seal 125 140 160 130 strength (° C.) Film Processing Parameters:Melt Temp (° F.) 445 431 423 429 Extruder Pressure (psi) 4810-48553970-4015 3050 4015-4055 Current (amp) 51 40 32 40 Voltage (V) 173 190183 193 spec. output (lb/hr/rpm) 2.381 2.50 2.56 2.44 Specific energy(w/lb/hr) 88.2 76.0 58.6 77.2 PPA additive (ppm) 250 250 200 —

As shown in Tables 2 and 5, the ethylene copolymer compositions (inv.1-6) have a melt flow ratio that is distinct from a resin prepared with(1,2-(n-propyl)(C₆F₅)Cp)Ti(N═P(t-Bu)₃)Cl₂ (comp. 1) and fromcommercially available EXCEED 1018CA™ (comp. 2). The inventive resins(see inv. 1-6) have a MFR (i.e. I₂₁/I₂) of greater than 30, while thecomparative resins 1 and 2 each have a melt flow ratio of less than 30.Further, the copolymer compositions having a fractional melt index (inv.1-5) have a similar MFR as an Enable 20-05™ resin having a fractionalmelt index (comp. 3), but a very different TREF profile. Similarly, acopolymer composition having a melt index of about 1.2 (inv. 6) has asimilar MFR as an Enable 20-10™ resin having a melt index of about 1.1(comp. 4), but a very different TREF profile. The TREF profile of theinventive resins is multimodal (bimodal or trimodal with two or threeprominent peaks separated by 5° C. or more), while the comp. resins 3and 4 each have a single peak evident in the TREF analysis. Theinventive resins 1-6 have a composition distribution breadth indexCDBI₅₀ of less than 75 wt % while comp. resins 3 and 4 each have aCDBI₅₀ of greater than 85%. Comparison of the inventive resins 1-6, withELITE resins (comparative examples 6 and 7) shows that although each mayhave a multimodal TREF profile (note: that the Elite resin is acopolymer of ethylene and 1-octene, and the inventive resin is acopolymer of ethylene and 1-hexene), the inventive resins 1-6 have abroader molecular weight distribution (Mw/Mn of greater than 4.0) and ahigher MFR (I₂₁/I₂ is greater than 32). The comparative resin 8, whichis DOWLEX 2045G, and is made using a Ziegler-Natta catalyst, has abimodal TREF profile and a MFR of less than 30.

When blown into film, inv. resins 1-5 have good dart impact values, goodstiffness, and are easy to process as indicated by the low shearthinning index (SHI) and the high specific output rates.

As shown in Tables 3 and 6, the dart impact of the fractional melt indexresins, inv. resins 1, 3-5 is typically more than 500 g/mil and arealmost as good as comp. resin 2, which has a much lower melt flow ratio(I₂₁/I₂). An exception is inv. resin 2 which has a dart impact of 438g/mil. The inv. resins 1, 3-5 also have a higher dart impact value thancomparative resins of similar melt index and/or melt flow ratio: comparefor example, comp. resin 3 (an Enable type resin) and comp. resin 5 (amelt blend of LLDPE and HPLDPE) which have dart impact values of 473g/mil and 317 g/mil respectively with inventive resins 1, 3, 4 and 5,which have a dart impact value of 638 g/mil, 887 g/mil, 542 g/mil and684 g/mil respectively.

Inventive resin 6 (which has a melt index I₂ of about 1.2 g/10 min), hasa somewhat lower dart impact at 225 g/mil than that of comp. resin 4 at286 g/mil (which has a similar melt index I₂), but this may be due tothe fact that it also has a higher density.

The stiffness of the inv. resins 1-5, as indicated by the 1% TD and MDsecant modulus is similar or higher relative to comparative resins 2, 3or 5. As shown in Tables 3 and 6, the inventive resins 1, 3-5 have a 1%MD secant modulus of greater than 190 MPa when blown into a ˜1 mil film.Comparative resins 2, 3 and 5 have a 1% MD secant modulus of 137, 187,and 167 MPa respectively when blown into a ˜1 mil film. Inv. resins 1-5have a 1% TD secant modulus of greater than 210 MPa when blown into a ˜1mil film. Comparative resins 2, 3 and 5 have a 1% TD secant modulus of166, 208 and 208 MPa respectively when blown into a ˜1 mil film. Asimilar comparison between inv. resin 6 (which has a melt index I₂ ofabout 1.2 g/10 min) with comp. resin 4 (which has a melt index I₂ of 1.1g/10 min), shows that inv. resin 6 has higher 1% TD and MD secantmodulus. Inv. resin 6 has a 1% MD secant modulus of 230 MPa and a 1% TDsecant modulus of 255 MPa, while comp. resin 4 has a 1% MD secantmodulus of 156 MPa and a 1% TD secant modulus of 171 MPa.

In terms of processability, the inventive resins 1-5 extrude with ahigher specific output rate at lower head pressure than comparativeresin 2 which has a lower melt flow ratio (see Tables 3 and 6).Inventive resins 1-5 have a similar specific output rate relative tocomp. resin 3, but generally at lower extruder head pressure (with inv.resin 3 being an exception). Comp. resin 5 is a melt blend comprising alinear low density resin LLDPE and 5 wt % of high pressure low densitypolyethylene (HPLDPE) resin which is known to impart improvedprocessability to a LLDPE due to the presence of long chain branching.Nevertheless, inventive resins 1-5 show higher specific output even atlower extruder head pressure than comparative resin 5 (see Tables 3 and6).

As can be seen in Table 2, the inventive resins having a fractional meltindex I₂, inventive resins 1-5 have a reverse comonomer distribution, amultimodal TREF profile, a CDBI₅₀ within a range of from 45 to 75 wt %,an MFR within a range of 32 to 50, a M_(w)/M_(n) within a range of from3.5 to 6.0 and a melt index I₂ of less than 1.0 g/10 min. Also shown inTable 2, inventive resin 6 has a reverse comonomer distribution, amultimodal TREF profile, a CDBI₅₀ within a range of from 45 to 75 wt %,an MFR within a range of 32 to 50, a M_(w)/M_(n) within a range of from3.5 to 6.0 and a melt index I₂ of about 1.2 g/10 min.

Each of the inventive resins 1-6 shown in Table 2 also have a broadunimodal molecular weight distribution (see FIG. 2 as representative ofthe inventive ethylene copolymers).

Representative TREF curves are shown in FIG. 1A for inventive resin 1and in FIG. 1B for inventive resin 3. A representative GPC curve isshown for Inventive resin 1 in FIG. 2. A representative GPC-FTIR curveis shown for inventive resin 1 in FIG. 3.

A van Gurp-Palmen analysis is a means by which to study a polymerarchitecture (e.g. molecular weight distribution, linearity, etc.) asreflected by the polymer melt morphology. A VGP curve is simply a plotof the phase angle (δ) versus complex modulus (G*), where the tworheology parameters are obtained using the frequency sweep test indynamic mechanical analysis (DMA). A shift of a VGP curve from abaseline curve or a decrease in the phase angles at the mid-range ofcomplex modulus may indicate changes in the polymer melt morphology.

A VGP plot allows for a determination of the crossover rheologyparameter which is defined as the intersecting point obtained betweenthe phase angle (δ) vs. complex modulus (G*) plot and a phase angle (δ)vs. complex viscosity (η*) plot. Based on a linear viscoelasticitytheory, the VGP crossover rheology parameter or “crossover phase angle”(δ^(XO)) occurs at a frequency (ω) which is equal to unity. It is thephase angle at which the G* and the η* are equivalent. Hence the VGPcrossover rheology parameter can be determined in a single DMA test.

The VGP crossover plots for resins sold under the trade-names Exceed1018CA (Comp. 2) and Enable (Comp. 3) are included in FIGS. 4A and 4Brespectively. The VGP crossover plots for the inventive resin 1 is shownin FIG. 4B. The VGP crossover plots for comparative resin 1, madeaccording to comparative example 1, are included in FIG. 4A. Finally,the resin sold under the trade name Elite 5400G (Comp. 7) is included inFIG. 4B. The VGP crossover points are dependent upon the copolymerarchitecture. Generally, for resins which are easier to process such asinventive copolymer 1 and comparative resin 3, the VGP phase angle atwhich crossover occurs defined as δ^(XO) is lower than for resins whichare more difficult to process such as comparative copolymers 1 and 2(compare FIGS. 4A and 4B). For resins that are easier to process, theshape of the phase angle-complex viscosity curves and the shape of thephase-angle complex modulus curves, are deflected somewhat and moreclosely resemble mirror images of each other, relative to the curvesobtained for resins which are more difficult to process (compare thecurves in FIG. 4A with the curves in FIG. 4B).

As shown in Table 2, all the inventive ethylene copolymers 1-6 alsosatisfy one or more of the following relationships:

(M _(w) /M _(n))≧72 [(I ₂₁ /I ₂)⁻¹+10⁻⁶(M _(n))];

δ^(XO) of from 55° to 70°;

δ^(XO)≦83.0−1.25(CDBI₅₀)/(M _(w) /M _(n)); and

δ^(XO)≦80.7−(CDBI₅₀)/(M _(w) /M _(n)) at a δ^(XO) of from 55° to 70°;

where δ^(XO) is the crossover phase angle, M_(w), M_(n), I₂₁, I₂ andCDBI₅₀ are all as defined as above. The data provided in Table 5, showsthat none of the comparative resins 1-8 satisfy the condition: i)(M_(w)/M_(n))≧72 [(I₂₁/I₂)⁻¹+10⁻⁶ (M_(n))] and that none of thecomparative resins 1-4, and 6-8 satisfy either of the conditions: ii)δ^(XO)≦83.0−1.25 (CDBI₅₀)/(M_(w)/M_(n)), or iii)δ^(XO)≦80.7−(CDBI₅₀)/(M_(w)/M_(n)) at a δ^(XO) of from 55° to 70°.

For further comparison purposes, inventive ethylene copolymers 1-6 havebeen plotted against several known commercial resins in FIG. 5. FIG. 5shows a plot of the equation: (M_(w)/M_(n))=72 [(I₂₁/I₂)⁻¹+10⁻⁶(M_(n))], as well as a plot of the M_(w)/M_(n) vs. 72 [(I₂₁/I₂)⁻¹+10⁻⁶(M_(n))] values for inv. resins 1-6 as well as several known commercialresins. The commercial resins included in FIG. 5 for comparison purposesare all resins having an melt index I₂ of 1.5 g/10 min or less and adensity of between 0.916 and 0.930 g/cm³ and which are sold under tradenames such as, Elite™, Exceed™, Marflex™, Starflex™ Dowlex™, SURPASS™,SCLAIR™, NOVAPOL™ and Enable™. As can be seen from FIG. 5, none of thesecommercial grades satisfy the condition: (M_(w)/M_(n))≧72[(I₂₁/I₂)⁻¹+10⁻⁶ (M_(n))]. In contrast all of the inv. resins 1-6satisfy the condition: (M_(w)/M_(n))≧72 [(I₂₁/I₂)⁻¹+10⁻⁶ (M_(n))]. Thiswork demonstrates the distinct architecture of the inventive ethylenecopolymers.

For further comparison purposes, inventive ethylene copolymers 1-6 havebeen plotted against several known commercial resins in FIG. 6. FIG. 6shows a plot of the equation: δ^(XO)=83.0−1.25 (CDBI₅₀)/(M_(w)/M_(n)),as well as a plot of the δ^(XO) vs. 83.0−1.25 (CDBI₅₀)/(M_(w)/M_(n))values for inv. resins 1-6 and several known commercial resins. Thecommercial resins included in FIG. 6 for comparison purposes are allresins having a melt index I₂ of 1.5 g/10 min or less and a density ofbetween 0.916 and 0.930 g/cm³ and which are sold under trade names suchas, Elite™, Exceed™, Marflex™, Starflex™ Dowlex™, SURPASS™, SCLAIR™,NOVAPOL™ and Enable™. As can be seen from the figure, none of thesecommercial grades satisfy the condition: δ^(XO)≦83.0−1.25(CDBI₅₀)/(M_(w)/M_(n)). In contrast, most of the inv. resins 1-6 satisfythe condition: δ^(XO)≦83.0−1.25 (CDBI₅₀)/(M_(w)/M_(n)). This workfurther demonstrates the distinct architecture of the inventive ethylenecopolymers.

For further comparison purposes, inventive ethylene copolymers 1-6 havebeen plotted against several known commercial resins in FIG. 7. FIG. 7shows a plot of the equation: δ^(XO)=80.7−(CDBI₅₀)/(M_(w)/M_(n)), aswell as a plot of the δ^(XO) vs. 80.7−(CDBI₅₀)/(M_(w)/M_(n)) values forinv. resins 1-6 and several known commercial resins. FIG. 7 also showswhich of the inventive and commercial resins have a δ^(XO) of from 55°to 70°. The commercial resins included in FIG. 7 for comparison purposesare all resins having an melt index I₂ of 1.5 g/10 min or less and adensity of between 0.916 and 0.930 g/cm³ and which are sold under tradenames such as, Elite™, Exceed™, Marflex™, Starflex™ Dowlex™, SURPASS™,SCLAIR™, NOVAPOL™ and Enable™. As can be seen from FIG. 7, none of thesecommercial grades satisfy the condition whereδ^(XO)≦80.7−(CDBI₅₀)/(M_(w)/M_(n)) at a δ^(XO) of from 55° to 70°. Incontrast all of the inv. resins 1-6 satisfy the condition whereδ^(XO)≦80.7−(CDBI₅₀)/(M_(w)/M_(n)) at a δ^(XO) of from 55° to 70°. Thiswork demonstrates the distinct architecture of the inventive ethylenecopolymers.

The present invention has been described with reference to certaindetails of particular embodiments thereof. It is not intended that suchdetails be regarded as limitations upon the scope of the inventionexcept insofar as and to the extent that they are included in theaccompanying claims.

What is claimed is:
 1. An ethylene copolymer comprising ethylene and analpha olefin having 3-8 carbon atoms, the ethylene copolymer having adensity of from about 0.916 g/cm³ to about 0.936 g/cm³, a melt index(I₂) of from about 0.1 g/10 min to about 2.0 g/10 min, a melt flow ratio(I₂₁/I₂) of from about 32 to about 50, a molecular weight distribution(M_(w)/M_(n)) of from about 3.6 to about 6.5, a reverse comonomerdistribution profile as determined by GPC-FTIR, a multimodal TREFprofile, and a composition distribution breadth index CDBI₅₀ of fromabout 45 wt % to about 75 wt % as determined by TREF, and which furthersatisfies the relationship: (M_(w)/M_(n))≧72 [(I₂₁/I₂)⁻¹+10⁻⁶ (M_(n))].2. The ethylene copolymer of claim 1 which further satisfies therelationship: δ^(XO)≦80.7−(CDBI₅₀)/(M_(w)/M_(n)) at a δ^(XO) of fromabout 55° to about 70°.
 3. The ethylene copolymer of claim 1 whichfurther satisfies the relationship: δ^(XO)≦83.0−1.25(CDBI₅₀)/(M_(w)/M_(n)).
 4. The ethylene copolymer of claim 2 whichfurther satisfies the relationship: δ^(XO)≦83.0−1.25(CDBI₅₀)/(M_(w)/M_(n)).
 5. The ethylene copolymer of claim 1 wherein theethylene copolymer has a CDBI₅₀ of from about 50 wt % to about 75 wt %.6. The ethylene copolymer of claim 1 wherein the ethylene copolymer hasa density of from about 0.917 g/cm³ to about 0.927 g/cm³.
 7. Theethylene copolymer of claim 1 wherein the ethylene copolymer has amolecular weight distribution (M_(w)/M_(n)) of from about 4.0 to about6.0.
 8. The ethylene copolymer of claim 1 wherein the copolymer has amultimodal TREF profile comprising two intensity maxima occurring atelution temperatures T(low) and T(high); wherein T(low) is from about65° C. to about 85° C. and T(high) is from about 90° C. to about 98° C.9. The ethylene copolymer of claim 1 wherein the alpha-olefin is1-hexene.
 10. The ethylene copolymer of claim 1 wherein the ethylenecopolymer has a Z-average molecular weight distribution (M_(z)/M_(w)) offrom about 2.0 to about 4.0.
 11. The ethylene copolymer of claim 1wherein the ethylene copolymer has a T(75)-T(25) of from about 5° C. toabout 20° C. as determined by TREF.
 12. An olefin polymerization processto produce an ethylene copolymer, the process comprising contactingethylene and at least one alpha olefin having from 3-8 carbon atoms witha polymerization catalyst system in a single gas phase reactor; theethylene copolymer having a density of from about 0.916 g/cm³ to about0.936 g/cm³, a melt index (I₂) of from about 0.1 g/10 min to about 2.0g/10 min, a melt flow ratio (I₂₁/I₂) of from about 32 to about 50, amolecular weight distribution (M_(w)/M_(n)) of from about 3.6 to about6.5, a reverse comonomer distribution profile as determined by GPC-FTIR,a multimodal TREF profile, a composition distribution breadth indexCDBI₅₀ of from about 50 wt % to about 75 wt % as determined by TREF andwhich satisfies the following relationship: (M_(w)/M_(n))≧72[(I₂₁/I₂)⁻¹+10⁻⁶ (M_(n))]; wherein the polymerization catalyst systemcomprises a single transition metal catalyst, a support, a catalystactivator, and a catalyst modifier; and wherein the single transitionmetal catalyst is a group 4 organotransition metal catalyst.
 13. Theolefin polymerization process of claim 12 wherein the group 4organotransition metal catalyst is a group 4 phosphinimine catalyst. 14.The olefin polymerization process of claim 13 wherein the group 4phosphinimine catalyst has the formula:(1-R²-Indenyl)Ti(N═P(t-Bu)₃)X₂; wherein R² is a substituted orunsubstituted alkyl group, a substituted or an unsubstituted aryl group,or a substituted or unsubstituted benzyl group, wherein substituents forthe alkyl, aryl or benzyl group are selected from the group consistingof alkyl, aryl, alkoxy, aryloxy, alkylaryl, arylalkyl and halidesubstituents; and wherein X is an activatable ligand.
 15. The olefinpolymerization process of claim 12 wherein the catalyst activator is analkylaluminoxane.
 16. The olefin polymerization process of claim 12wherein the catalyst modifier comprises at least one long chain aminecompound.
 17. The olefin polymerization process of claim 12 wherein theethylene copolymer further satisfies the relationship:δ^(XO)≦80.7−(CDBI₅₀)/(M_(w)/M_(n)) at a δ^(XO) of from about 55° toabout 70°.
 18. The olefin polymerization process of claim 12 wherein theethylene copolymer further satisfies the relationship: δ^(XO)≦83.0−1.25(CDBI₅₀)/(M_(w)/M_(n)).
 19. The olefin polymerization process of claim17 wherein the ethylene copolymer further satisfies the relationship:δ^(XO)≦83.0−1.25 (CDBI₅₀)/(M_(w)/M_(n)).
 20. A film layer having a dartimpact of greater than about 200 g/mil, a about 1% MD secant modulus ofgreater than about 140 MPa, a about 1% TD secant modulus of greater thanabout 175 MPa and a ratio of MD tear to TD tear of about 0.75 or less,wherein the film layer comprises an ethylene copolymer having a densityof from about 0.916 g/cm³ to about 0.930 g/cm³, a melt index (I₂) offrom about 0.1 g/10 min to about 2.0 g/10 min, a melt flow ratio(I₂₁/I₂) of from about 32 to about 50, a molecular weight distribution(M_(w)/M_(n)) of from about 3.6 to about 6.5, a reverse comonomerdistribution profile as determined by GPC-FTIR, a multimodal TREFprofile, a composition distribution breadth index CDBI₅₀ of from about50 wt % to about 75 wt % as determined by TREF, and which satisfies thefollowing relationship: (M_(w)/M_(n))≧72 [(I₂₁/I₂)⁻¹+10⁻⁶ (M_(n))]. 21.The film layer of claim 20, wherein the film layer has a ratio of MDtear to TD tear of about 0.45 or less.
 22. The film layer of claim 20,wherein the film layer has a dart impact of greater than about 500g/mil.
 23. The film layer of claim 20, wherein the ethylene copolymerfurther satisfies the relationship: δ^(XO)≦80.7−(CDBI₅₀)/(M_(w)/M_(n))at a δ^(XO) of from about 55° to about 70°.
 24. The film layer of claim20, wherein the ethylene copolymer further satisfies the relationship:δ^(XO)≦83.0−1.25 (CDBI₅₀)/(M_(w)/M_(n)).
 25. The film layer of claim 23,wherein the ethylene copolymer further satisfies the relationship:δ^(XO)≦83.0−1.25 (CDBI₅₀)/(M_(w)/M_(n)).